Name

NAKAI, Hiromi

Official Title

Professor

AffiliationFaculty of Science and Engineering

(School of Advanced Science and Engineering)

Contact Information

Mail Address

Mail Address
nakai@waseda.jp

Address・Phone Number・Fax Number

Address
Department of Chemistry, Faculty of Science and Engineering, Waseda University 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Phone Number
+81-3-5286-3452
Fax Number
+81-3-3205-2504

URL

Web Page URL

http://www.chem.waseda.ac.jp/lab/nakai/index.htm

http://www.chem.waseda.ac.jp/lab/nakai/

Grant-in-aids for Scientific Researcher Number
00243056

Sub-affiliation

Sub-affiliation

Faculty of Science and Engineering(Graduate School of Advanced Science and Engineering)

Faculty of Science and Engineering(School of Science and Engineering)

Affiliated Institutes

理工学総合研究センター

兼任研究員 1989-2006

実践的ナノ化学G

研究所員 2007-2011

理工学術院総合研究所(理工学研究所)

兼任研究員 2006-2018

理工学術院総合研究所(理工学研究所)

兼任研究員 2018-

Educational background・Degree

Educational background

-1987 Kyoto University Faculty of Engineering
-1992 Kyoto University Graduate School, Division of Engineering

Career

1992/05-1996/03Research Associate, Kyoto Univ.
1996/04-1998/03Assistant Professor, Waseda Univ.
1998/04-2004/03Associate Professor, Waseda Univ.
2004/04-2006/03Professor, Waseda Univ.
2006/04-Collaborative Researcher, The Institute of Physical
1997/02-2005/03and Chemical Research.(Concurrrent)
1997/04-1998/03Visiting Lecturer, Kyoto Univ.(Concurrent)
2002/10-2003/10Visiting Professor, Rice Univ.(Concurrent)

Academic Society Joined

Chemical Society of Japan

Japan Society for Molecular Science

Society of Computer Chemistry, Japan

Catalysis Society of Japan

American Physical Society

American Chemical Society

The World Association of Theoretically Oriented Chemists (WATOC)

Asia-Pacific Association of Theoretical & Computational Chemists (APATCC)

OfficerCareer(Outside the campus)

2007-2008ICQC-XII Local Committee ()
2007-QSCP-XV International Scientific Committee ()
2008-ISTCP-VII Chair ()
2009-QSCP-XVI Local Committee ()
2010-2011QSCP-XVII International Scientific Committee ()
2010-CJK-WTCC Stering Committee ()

Award

The 2011 Pople Medal

2011

QSCP Promising Scientist Award of Centre de Mecanique Ondulatoire Appliquee

2006/08

Japan Association of Aerosol Science and Technology Best Paper Award.

2002

Research Field

Grants-in-Aid for Scientific Research classification

Chemistry / Basic chemistry / Physical chemistry

Chemistry / Basic chemistry / Physical chemistry

Research interests Career

Development of Nonadiabatic Molecular Theory and Its Application to Phenomena Related with Nuclear Quantum Process

Current Research Theme Keywords:Nonadiabatic Effect, Quantum Effect, Nuclear Motion

Individual research allowance

Quantum Chemistry in Catalytic Activity on Surface

Current Research Theme Keywords:Quantum-Chemistry,Catalytic-Activity,Metal-Surface

Cooperative Research within institute

Paper

Accelerating convergence in the antisymmetric product of strongly orthogonal geminals method

M. Tarumi, M. Kobayashi1, H. Nakai

Int. J. Quantum Chem. 2012-

DOI

Constrained self-consistent field method revisited toward theoretical designs of functional materials under external field

Y. Yamagata, Y. Imamura, H. Nakai

Chem. Phys. Lett. 521p.132 - 1362012-

DOI

Description of Core Ionized and Excited States by Density Functional Theory and Time-dependent Density Functional Theory

Y. Imamura, H. Nakai

Advances in the Theory of Atomic and Molecular Systems 2012-

Development of the explicitly correlated Gaussian-nuclear orbital plus molecular orbital theory: Incorporation of electron-electron correlation

H. Nishizawa, Y. Imamura, Y. Ikabata, H. Nakai

Chem. Phys. Lett. 533p.100 - 1052012-

DOI

Direct alkoxysilylation of alkoxysilanes for the synthesis of explicit alkoxysiloxane oligomers

R. Wakabayashi, M. Tamai, K. Kawahara, H. Tachibana, Y. Imamura, H. Nakai, K. Kuroda

J. Organometallic Chem. 716p.26 - 312012-

DOI

Divide-and-conquer based quantum chemical study for interaction between HIV-1 reverse transcriptase and MK-4965 inhibitor

P. Saparpakorn, M. Kobayashi1, S. Hannongbua, H. Nakai

Int. J. Quantum Chem. 2012-

DOI

Divide-and-conquer electronic-structure study on the mechanism of the West Nile Virus NS3 protease inhibitor

P. Saparpakorn, M. Kobayashi, H. Nakai

Bull. Chem. Soc. Jpn. 2012-

Divide-and-conquer-based symmetry adapted cluster method: Synergistic effect of subsystem fragmentation and configuration selection

T. Yoshikawa, M. Kobayashi1, H. Nakai

Int. J. Quantum Chem. 2012-

DOI

Dynamic hyperpolarizability calculations of large systems: the linear-scaling divide-and-conquer approach

M. Kobayashi, T. Touma, H. Nakai

J. Chem. Phys. 136(8) p.084108 1 - 102012-

DOI

Evaluation of electron-repulsion integral of the explicitly correlated Gaussian-nuclear orbital plus molecular orbital theory

H. Nishizawa, M. Hoshino, Y. Imamura, H. Nakai

Chem. Phys. Lett. 521p.142 - 1492012-

DOI

Extension of local response dispersion method to excited state calculation based on time-dependent density functional theory

Y. Ikabata, H. Nakai

J. Chem. Phys. 2012-

How does it become possible to treat delocalized and/or open-shell systems in fragmentation-based linear-scaling electronic structure calculation: the case of divide-and-conquer method

M. Kobayashi, H. Nakai

Phys. Chem. Chem. Phys. 2012-

Linearity condition for orbital energies in density functional theory (IV): Determination of range-determining parameter

Y. Imamura, R. Kobayashi, H. Nakai

Int. J. Quantum Chem. 2012-

DOI

Local unitary transformation method for large-scale two-component relativistic calculations: Case for a one-electron Dirac Hamiltonian

J. Seino, H. Nakai

J. Chem. Phys. 136(24) p.244102 1 - 132012-

DOI

Self-consistent field treatment and analytical energy gradient of local response dispersion method

Y. Ikabata, T. Sato, H. Nakai

Int. J. Quantum Chem. 2012-

DOI

Theoretical analysis of adsorption structure of hydrated hypophosphite ion on Pd (111) surface

M. Kunimoto, K. Seki, H. Nakai, T. Homma

Electrochemistry 2012-

DOI

化学原理の発見:縮重系励起の対称則

H. Nakai

J. Comput. Chem. Jpn. 11(1) p.1 - 122012-

Bond energy analysis revisited and designed toward a rigorous methodology

H. Nakai, H. Ohashi, Y. Imamura, Y. Kikuchi

J. Chem. Phys. 135(12) p.124105 1 - 122011-

DOI

Density functional theory analysis for orbital interaction between hypophosphite ions and metal surfaces

M. Kunimoto, H. Nakai, T. Homma

J. Electrochem. Soc. 158(10) p.D626 - D6332011-

DOI

Density functional theory analysis of reaction mechanism of hypophosphite ions on metal surfaces

M. Kunimoto, T. Shimada, S. Odagiri, H. Nakai, T. Homma

J. Electrochem. Soc. 158(9) p.D585 - D5892011-

DOI

Divide-and-conquer approaches to quantum chemistry: Theory and implementation

M. Kobayashi, H. Nakai

Linear-Scaling Techniques in Computational Chemistry and Physics: Methods and Applications Springer,2011p.99 - 1272011-

Energy expression of the chemical bond between atoms in metal oxides

Y. Shinzato, Y. Saito, M. Yoshino, H. Yukawa, M. Morinaga, T. Baba, H. Nakai

J. Phys. Chem. Solids 72p.853 - 8612011-

DOI

Finite-field evaluation of static (hyper)polarizabilities based on the linear-scaling divide-and-conquer method

T. Touma, M. Kobayashi, H. Nakai

Theor. Chim. Acta. 130(4〜6) p.701 - 7092011-

DOI

Interpretation of intermolecular geometric isotope effect in hydrogen bonds: nuclear orbital plus molecular orbital study

Y. Ikabata, Y. Imamura, H. Nakai

J. Phys. Chem. 115(8) p.1433 - 14392011-

DOI

Linear-scaling divide-and-conquer second-order M?ller-Plesset perturbation calculation for open-shell systems: Implementation and application

T. Yoshikawa, M. Kobayashi, H. Nakai

Theor. Chim. Acta. 130(2〜3) p.411 - 4172011-

DOI

Linearity condition for orbital energies in density functional theory (II): Application to global hybrid functional

Y. Imamura, R. Kobayashi, H. Nakai

Chem. Phys. Lett. 513(1〜3) p.130 - 1352011-

DOI

Linearity condition for orbital energies in density functional theory: Construction of orbital-specific hybrid functional

Y. Imamura, R. Kobayashi, H. Nakai

J. Chem. Phys. 134(12) p.124113 1 - 62011-

DOI

Reconsidering an analytical gradient expression within a divide-and-conquer self-consistent field approach: exact formula and its approximate treatment

M. Kobayashi, T. Kunisada, T. Akama, D. Sakura, H. Nakai

J. Chem. Phys. 134(3) p.34105 1 - 112011-

DOI

Rigorous non-Born-Oppenheimer theory: Combination of explicitly correlated Gaussian method and nuclear orbital plus molecular orbital theory

M. Hoshino, H. Nishizawa, H. Nakai

J. Chem. Phys. 135(2) p.024111 1 - 132011-

DOI

Theoretical analysis on catalytic activity of metal surfaces on reaction of hypophosphite ion

M. Kunimoto, H. Nakai, T. Homma

J. Electrochem. Soc. 80(3) p.1 - 62011-

DOI

Theoretical design of hexacoordinate hypervalent carbon compounds by analyzing substituent effec

H. Nakai, M. Okoshi, T. Atsumi, Y. Kikuchi, K.-y. Akiba

Bull. Chem. Soc. Jpn. 84(5) p.505 - 5102011-

DOI

Two-level hierarchical parallelization of second-order M?ller?Plesset perturbation calculations in divide-and-conquer method

M. Katouda, M. Kobayashi, H. Nakai, S. Nagase

J. Comput. Chem. 32(13) p.2756 - 27642011-

DOI

ナノ科学のための分割統治量子化学計算法

小林正人,中井浩巳

ナノ学会会報「次世代スパコン特集」 9(2) p.85 - 892011-

巨大分子系の量子化学法

中井浩巳

CSJカレントレビュー・シリーズ第8巻「巨大分子系の計算化学-超大型計算機時代の理論化学の新展開」 p.52 - 602011-

炭素原子の電子配置

中井浩巳

『炭素学』 p.19 - 382011-

理論化学における理論の革新

中井浩巳

「化学のブレークスルー」 p.159 - 1632011-

量子化学に基づく原子・分子のシミュレーション

中井浩巳, 大越昌樹

日本シミュレーション学会誌「シミュレーション」 30(4) p.5 - 122011-

Acceleration of self-consistent-field convergence in ab initio molecular dynamics and Monte Carlo simulations and geometry optimization

T. Atsumi, H. Nakai

Chem. Phys. Lett. 490(1〜3) p.102 - 1082010-

DOI

Application of real-time time-dependent density functional theory with the CV-B3LYP functional to core excitations

T. Akama, Y. Imamura, H. Nakai

Chem. Lett. 39(4) p.407 - 4092010-

DOI

Divide-and-conquer self-consistent field calculation for open-shell systems: Implementation and application

M. Kobayashi, T. Yoshikawa, H. Nakai

Chem. Phys. Lett. 500(1〜3) p.172 - 1772010-

DOI

Generalized M?ller?Plesset partitioning in multiconfiguration perturbation theory

M. Kobayashi, A. Szabados, H. Nakai, P. Surjan

J. Chem. Theory Comp. 6(7) p.2024 - 20332010-

DOI

Local response dispersion method II. Generalized multicenter interactions

T. Sato, H. Nakai

J. Chem. Phys. 133(19) p.194101 1 - 92010-

DOI

Quantitative evaluation of catalytic effect of metal chlorides on the decomposition reaction of NaAlH4

H. Hirate, Y. Saito, I. Nakaya, H. Sawai, H. Yukawa, M. Morinaga, H. Nakai

Int. J. Quant. Chem. 109(12) p.2793 - 28002010-

DOI

Short-time Fourier transform analysis of real-time time-dependent Hartree-Fock and time-dependent density functional theory calculations with Gaussian basis functions

T. Akama, H. Nakai

J. Chem. Phys. 132(5) p.054104 1 - 112010-

DOI

Theoretical study of hypervalent bonds in 1,6-diaza-1,6-dihydro- and 1,6-dihydro-1,6-dioxapentalene systems with a heteroatom X at 6s position (X = 14-16 group atoms)

T. Atsumi, T. Abe, K.-y. Akiba, H. Nakai

Bull. Chem. Soc. Jpn. 83(8) p.892 - 8992010-

DOI

Theoretical study on bond-switching in 1,6-dihydro-6a-thia-1,6-diazapentalene (10-S-3) systems compared with corresponding oxygen analogues

T. Atsumi, T. Abe, K.-y. Akiba, H. Nakai

Bull. Chem. Soc. Jpn. 83(5) p.520 - 5292010-

DOI

Time-dependent Hartree-Fock frequency-dependent polarizability calculation applied to divide-and-conquer electronic structure method

T. Touma, M. Kobayashi, H. Nakai

Chem. Phys. Lett. 485(1〜3) p.247 - 2522010-

DOI

Unusual energy balance between atoms in post-perovskite MgSiO3

H. Hirate, H. Sawai, Y. Saito, H. Yukawa, M. Morinaga, H. Nakai

J. Am. Ceram. Soc. 93(10) p.3449 - 34542010-

DOI

理論化学における理論の革新

中井浩巳

別冊化学「化学のブレークスルー【理論化学編】」 p.66 - 722010-

Density functional method including weak interactions: dispersion coefficients based on the local response approximation

T. Sato, H. Nakai

J. Chem. Phys. 131(22) p.224104 1 - 122009-

DOI

Density functional study for sugar-base correlation of nucleoside cytidine and its fragments

S. Saha, F. Wang, T, Tsuchimochi, A. Nakata, Y. Imamura, H. Nakai

Bull. Chem. Soc. Jpn. 82(2) p.187 - 1952009-

DOI

Divide-and-conquer-based linear-scaling approach for traditional and renormalized coupled cluster methods with single, double, and noniterative triple excitations

M. Kobayashi, H. Nakai

J. Chem. Phys. 131(11) p.114108 1 - 92009-

DOI

Dual-level hierarchical scheme for linear-scaling divide-and-conquer correlation theory

M. Kobayashi, H. Nakai

Int. J. Quant. Chem. 109(10) p.2227 - 22372009-

DOI

Electronic temperature in divide-and-conquer electronic structure calculation revisited: Assessment and improvement of self-consistent field convergence

T. Akama, M. Kobayashi, H. Nakai

Int. J. Quant. Chem 109(12) p.2706 - 27132009-

DOI

Extension of density functional theory to nuclear orbital plus molecular orbital theory: Self-consistent field calculations with the Colle-Salvetti electron-nucleus correlation functional

Y. Imamura, Y. Tsukamoto, H. Kiryu, H. Nakai

Bull. Chem. Soc. Jpn. 82(9) p.1133 - 11392009-

DOI

Extension of energy density analysis to periodic-boundary-condition calculations with plane-wave basis functions

Y. Imamura, A. Takahashi, T. Okada, T. Ohno, H. Nakai

Phys. Rev. B, 81(11) p.115136 1 - 72009-

DOI

Extension of frozen orbital analysis to the Tamm-Dancoff approximation to time-dependent density functional theory

Y. Imamura, T. Baba, H. Nakai

Chem. Lett. 38(6) p.528 - 5292009-

DOI

Implementation of divide-and-conquer (DC) electronic structure code to GAMESS program package

M. Kobayashi, T. Akama, H. Nakai

J. Comput. Chem. Jpn. 8(1) p.1 - 122009-

DOI

Observation by UV-visible and NMR spectroscopy and theoretical confirmation of 4-isopropyltropolonate ion, 4-isopropyltropolone (hinokitiol), and protonated 4-isopropyltropolone in acetonitrile

M. Hojo, T. Ueda, M. Ike, K. Okamura, T. Sugiyama, M. Kobayashi, H. Nakai

J. Chem. Eng. Data 55(5) p.1986 - 19892009-

DOI

One-body energy decomposition schemes revisited: Assessment of Mulliken-, grid-, and conventional energy density analyses

Y. Kikuchi, Y. Imamura, H. Nakai

Int. J. Quant. Chem. 109(11) p.2464 - 24732009-

DOI

Quantitative approach to the understanding of catalytic effect of metal oxides on the desorption reaction of MgH2

H. Hirate, Y. Saito, I. Nakaya, H. Sawai, H. Yukawa, M. Morinaga, T. Baba, H. Nakai

Int. J. Quant. Chem. 109(12) p.2793 - 28002009-

DOI

Rules for excited states of degenerate systems: Interpretation by frozen orbital analysis

H. Nakai

Advances in the Theory of Atomic and Molecular Systems: Conceptual and Computational Advances in Quantum Chemistry’ Progress in Theoretical Chemistry and Physics p.363 - 3952009-

UV-visble, 1H and 13C NMR spectroscopic studies on the interaction between protons or alkaline earth metal ions and the benzoate ion in acetonitrile

M. Hojo, T. Ueda, M. Ike, M. Kobayashi, H. Nakai

J. Mol. Liquids 145(3) p.152 - 1572009-

DOI

インシリコ・ケミストリー〜高性能量子化学計算環境の構築〜

中井浩巳

早稲田産学連携レビュー2009 p.76 - 772009-

化学の領域を広げる巨大分子の電子状態計算

小林正人,中井浩巳

化学 64(1) p.38 - 422009-

Analysis on excitations of molecules with Ih symmetry: Frozen orbital analysis and general rules

T. Baba, Y. Imamura, M. Okamoto, H. Nakai

Chem. Lett 37(3) p.322 - 3232008-

DOI

Application of the Sakurai-Sugiura projection method to core-excited-state calculation by time-dependent density functional theory

T. Tsuchimochi, M. Kobayashi, A. Nakata, Y. Imamura

J. Comput. Chem. 29(14) p.2311 - 23162008-

DOI

Colle-Salvetti-Type Correction for Electron-Nucleus Correlation in the Nuclear Orbital Plus Molecular Orbital Theory

Y. Imamura, H. Kiryu, H. Nakai

J. Comput. Chem. 29(5) p.735 - 7402008-

DOI

Determination of active sites based on unified analysis of potential energy profile in chemical reaction: application to C-H activation of methane by Ti(IV)-imido complex

H. Nakai, J. Suzuki, Y. Kikuchi

Chem. Phys. Lett. 460(1〜3) p.347 - 3512008-

DOI

Development of linear scaling techniques based on divide-and-conquer method

H. Nakai, T. Akama, M. Kobayashi

Bull. Soc. Discrete Variational Xα 21(1,2) p.47 - 542008-

Discovery of hexacoordinate hypervalent carbon compounds: Density functional study

Y. Kikuchi, M. Ishii, K.-y. Akiba, H. Nakai

Chem. Phys. Lett 460(1〜3) p.37 - 412008-

DOI

Energy density analysis for second-order Møller-Plesset perturbation theory and coupled cluster theory with singles and doubles: Applications to C2H4-CH4 complexes

Y. Imamura, H. Nakai

J. Comput. Chem 29(10) p.1555 - 15632008-

DOI

Estimation of redox potential of strained Si by density functional theory calculation

K. Sakata, S. Ishizaki, H. Nakai, T. Homma

J. Phys. Chem. C 112(10) p.3538 - 35422008-

DOI

Extension of linear-scaling divide-and-conquer-based correlation method to coupled cluster theory with singles and doubles excitations

M. Kobayashi, H. Nakai

J. Chem. Phys. 129(4) p.044103 1 - 92008-

DOI

Molecular orbital propagation to accelerate self-consistent-field convergence in an ab initio molecular dynamics simulation

T. Atsumi, H. Nakai

J. Chem. Phys. 128(9) p.094101 1 - 92008-

DOI

Natural bond orbital based energy density analysis for correlated methods: Second-order M?ller-Plesset perturbation and coupled-cluster singles and doubles

Y. Imamura, T. Baba, H. Nakai

Int. J. Quant. Chem. 108(8) p.1316 - 13252008-

DOI

New expression of the chemical bond in hydrides using atomization energies

Y. Shinzato, H. Yukawa, M. Morinaga, T. Baba, H. Nakai

Adv. Quant. Chem. 54p.145 - 1602008-

エネルギー密度解析による表面モデルの検証および触媒作用の解明

中井浩巳, 菊池那明, 今村穣

触媒 50(7) p.601 - 6072008-

メソ物質設計のための線形スケーリング量子化学計算

中井浩巳

化学と工業 61(10) p.9612008-

Hybrid treatment combining the translation- and rotation-free nuclear orbital plus molecular orbital theory with generator coordinate method: TRF-NOMO/GCM

K. Sodeyama, H. Nishizawa, M. Hoshino, M. Kobayashi, H. Nakai

Chem. Phys. Lett. 433(4〜6) p.409 - 4152007/04-

DOI

Analysis of self-interaction correction for describing core excited states

Y. Imamura, H. Naka

Int. J. Quant. Chem. 107(1) p.23 - 292007/01-

DOI

Grid-Based Energy Density Analysis: Implementation and Assessment

Y. Imamura, A. Takahashi, H. Nakai

J. Chem. Phys. 126(3) p.034103 1 - 102007/01-

DOI

A unified approach to the analysis of the chemical bond in hydrides and hydrocarbons

Y. Shinzato, H. Yukawa, M. Morinaga, T. Baba, H. Nakai

Acta Mater. 55(20) p.6673 - 66802007-

DOI

Ab Initio Molecular Dynamics Simulation of Energy Relaxation Process of Protonated Water Dimer

Y. Yamauchi, S. Ozawa, H. Nakai

J. Phys. Chem. A, 111(11) p.2062 - 20662007-

DOI

Alternative Linear-Scaling Methodology for the Second-Order Møller-Plesset Perturbation Calculation Based on the Divide-and-Conquer Method

M. Kobayashi, Y. Imamura, H. Nakai

J. Chem. Phys. 127(7) p.074103 1 - 82007-

DOI

Application of Bond Energy Density Analysis (Bond-EDA) to Diels-Alder Reaction

T. Baba, M. Ishii, Y. Kikuchi, H. Nakai

Chem. Lett. 36(5) p.616 - 6172007-

DOI

Density Functional Theory Study on the Reaction Mechanism of Reductants for Electroless Ag Deposition Process

T. Shimada, H. Nakai, T. Homma

J. Electrochem. Soc. 154(4) p.D273 - D2762007-

DOI

Description of Core Excitations by Time-Dependent Density Functional Theory with LDA, GGA, Meta-GGA, and Hybrid Functionals

Y. Imamura, T. Otsuka, H. Nakai

J. Comput. Chem. 28(12) p.2067 - 20742007-

DOI

Development of Analytic Energy Gradient Method in Nuclear Orbital Plus Molecular Orbital Theory

M. Hoshino, Y. Tsukamoto, H. Nakai

Int. J. Quant. Chem. 107(14) p.2575 - 25852007-

DOI

Energy Density Analysis of the Chemical Bond between Atoms in Perovskite-Type Hydrides

Y. Shinzato, H. Yukawa, M. Morinaga, T. Baba, H. Nakai,

J. Alloys Compd. 446-447p.96 - 1002007-

DOI

Extension of Energy Density Analysis to Periodic-Boundary-Condition Calculation: Evaluation of Locality in Extended Systems

H. Nakai, Y. Kurabayashi, M. Katouda, T. Atsumi

Phys. Lett. 438(1〜3) p.132 - 1382007-

DOI

Extension of the Core-Valence-Rydberg B3LYP Functional to Core-Excited-State Calculations of Third-Row Atoms

A. Nakata, Y. Imamura, H. Nakai

J. Chem. Theory Comput. 3(4) p.1295 - 13052007-

DOI

Implementation of Divide-and-Conquer Method Including Hartree-Fock Exchange Interaction

T. Akama, M. Kobayashi, H. Nakai

J. Comput. Chem. 28(12) p.2003 - 20122007-

DOI

Is the divide-and-conquer Hartree-Fock method valid for calculations of delocalized systems?

T. Akama, A. Fujii, M. Kobayashi, H. Nakai

Mol. Phys. 19-22p.2799 - 28042007-

DOI

Isotope Effect in Dihydrogen-Bonded Systems: Application of Analytical Energy Gradient Method in the Nuclear Orbital Plus Molecular Orbital Theory

H. Nakai, Y. Ikabata, Y. Tsukamoto, Y. Imamura, K. Miyamoto, M. Hoshino

Mol. Phys. 105(19〜22) p.2649 - 26572007-

DOI

Molecular Orbital Study on the Oxidation Mechanism of Hydrazine and Hydroxylamine as Reducing Agents for Electroless Deposition Process

T. Shimada, A. Tamaki, H. Nakai, T. Homma

Electrochemistry 75(1) p.45 - 492007-

New Expression of the Chemical Bond in Perovskite-Type Oxides

Y. Shinzato, Y. Saito, H. Yukawa, M. Morinaga, T. Baba, and H. Nakai

Mater. Sci. Forum 561-565(PRICM 6) p.1823 - 18262007-

DOI

Nuclear orbital plus molecular orbital (NOMO) theory: Simultaneous determination of nuclear and electronic wave functions without Born-Oppenheimer approximation

H. Nakai

Int. J. Quant. Chem. (Review) 107(14) p.2849 - 28692007-

Theoretical Design of Monofunctional Psoralen Compounds in Photochemotherapy

A. Nakata, T. Baba, H. Nakai

Bull. Chem. Soc. Jpn. 80(7) p.1341 - 13492007-

DOI

Theoretical Determination of Hypervalent Bond Energy of 10-S-3 Sulfurane Derivatives

Y. Yamauchi, K.-y. Akiba, H. Nakai,

Chem. Lett. 36(9) p.1120 - 11212007-

DOI

UV-Visible and 1H or 13C NMR Spectroscopic Studies on the Specific Interaction between Lithium Ions and the Anion from Tropolone or 4-Isopropyltropolone (Hinokitiol) and on the Formation of Protonated Tropolones in Acetonitrile or Other Solvents

M. Hojo, T. Ueda, T. Inoue, M. Ike, M. Kobayashi, H. Nakai

J. Phys. Chem. B,111(7) p.1759 - 17682007-

DOI

Wavelet Transform Analysis of Ab Initio Molecular Dynamics Simulation: Application to Core-Excitation Dynamics of BF3

T. Otsuka, H. Nakai

J. Comput. Chem. 28(6) p.1137 - 11442007-

DOI

原子核と電子の波動関数を同時に決定するためのnon-Born-Oppenheimer理論:NOMO理論

中井浩巳, 星野稔

Mol. Sci. (分子科学) 1p.A0010 1 - 222007-

表面-分子相互作用系の量子化学計算に関する最近の動向

中井浩巳

表面科学 28(3) p.150 - 1592007-

Elimination of translational and rotational motions in nuclear orbital plus molecular orbital theory: Contribution of the first-order rovibrationa coupling

K. Miyamoto, M. Hoshino, H. Nakai

J. Chem. Theory Comp. 2(6) p.1544 - 15502006/11-

DOI

Second-order Møller-Plesset perturbation energy obtained from divide-and-conquer Hartree-Fock density matrix

M. Kobayashi, T. Akama, H. Nakai

J. Chem. Phys 125(20) p.204106 1 - 82006/11-

DOI

Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-Valence-Rydberg B3LYP

A. Nakata, Y. Imamura, H. Nakai

J. Chem. Phys. 125(6) p.064109 1 - 92006/08-

DOI

Energy density analysis of cluster size dependence of surface-molecule interactions (II): Formate adsorption onto a Cu (111) surface

H. Nakai, Y. Kikuchi

J. Comp. Chem. 27(8) p.917 - 9252006/06-

DOI

Natural atomic orbital-based energy density analysis: implementation and assessmen

T. Baba, M. Takeuchi, H. Nakai

Chem. Phys. Lett 424(1〜3) p.193 - 1982006/06-

DOI

Elimination of translational and rotational motions in nuclear orbital plus molecular orbital theory: Application of Møller-Plesset perturbation theory

M. Hoshino, H. Nakai

J. Chem. Phys. 124(19) p.194110 1 - 102006/05-

DOI

Non-Born-Oppenheimer effects predicted by translation-free nuclear orbital plus molecular orbital method

K. Sodeyama, K. Miyamoto, H. Nakai

Chem. Phys. Lett. 421(1〜3) p.72 - 762006/04-

DOI

Implementation of Surján’s density matrix formulae for calculating second-order Møller-Plesset energy

M. Kobayashi, H. Nakai

Chem. Phys. Lett. 420(1〜3) p.250 - 2552006/03-

DOI

Time-dependent density functional theory calculations for core excited states: Assessment of standard exchange-correlation functionals and development of a novel hybrid functional

A. Nakata, Y. Imamura, T. Otsuka, H. Nakai

J. Chem. Phys. 124(9) p.094105 1 - 92006/03-

DOI

Time-dependent density functional theory (TDDFT) calculations for core-excited states: Assessment of an exchange functional combining the Becke88 and van Leeuwen-Baerends-type functionals

Y. Imamura, H. Nakai

Chem. Phys. Lett. 419(1〜3) p.297 - 3032006/02-

DOI

Periodic-boundary-condition calculation using Heyd-Scuseria-Ernzerhof screened Coulomb hybrid functional: Electronic structure of anatase and rutile TiO<SUB>2</SUB>

H. Nakai, J. Heyd, G. E. Scuseria

J. Comput. Chem. Jpn. 5(1) p.7 - 182006/01-

Reply to "Comment on `Elimination of translational and rotational motions in nuclear orbital plus molecular orbital theory'"

H. Nakai, M. Hoshino, K. Miyamoto, and S. Hyodo

J. Chem. Phys. 123p.2371022005/12-

DOI

Energy Density Analysis of Kohn-Sham DFT Method and Its Applications

T. Baba, Y. Yamauchi, Y. Kikuchi, Y. Kurabayashi, H. Nakai

Bull. Soc. Discrete Variational Xα. 18(1) p.7 - 192005/12-

Characterization of strained Si wafer surface by density functional theory analysis

K. Sakata, T. Homma, H. Nakai, T. Osaka

, Electrochimica Acta 51(5) p.1000 - 10032005/11-

DOI

Density functional theory study on the oxidation mechanisms of aldehydes as reductants for electroless Cu deposition process

T. Shimada, K. Sakata, T. Homma, H. Nakai, T. Osaka

Electrochimica Acta 51(5) p.906 - 9152005/11-

DOI

Synthesis of the Pivalamidate-Bridged Pentanuclear Platinum(II,III) Linear Complexes with Pt···Pt Interactions

S. Arai, M. Ochiai, W. Chen, A. Nakata, H. Nakai, K. Matsumoto

Inorg. Chem. 44(23) p.8552 - 85602005/11-

DOI

Energy Density Analysis of Embedded Cluster Models for an MgO crystal

Y. Kawamura, H. Nakai

Chem. Phys. Lett. 410(1〜3) p.64 - 692005/07-

DOI

Hybrid approach for ab initio molecular dynamics simulation combining energy density analysis and short-time Fourier transform: Energy transfer spectrogram

Y. Yamauchi, H. Nakai

J. Chem. Phys. 123(3) p.034101 1 - 92005/07-

DOI

Principal component analysis with energy density of Calophyllum coumarins

M. Takeuchi, A. Nakata, H. Nakai

Chem. Lett. 34(6) p.844 - 8452005/06-

DOI

Elimination of translational and rotational motions in nuclear orbital plus molecular orbital theory

H. Nakai, M. Hoshino, K. Miyamoto, S. Hyodo

J. Chem. Phys. 122(22) p.16101 1 - 102005/05-

DOI

Short-time Fourier transform Analysis of Ab Initio Molecular Dynamics Simulation : Collision Reaction between CN and C4H6

M. Tamaoki, Y. Yamauchi, H. Nakai

J. Comp. Chem. 26(5) p.436 - 4422005/04-

DOI

Extension of energy density analysis to treating chemical bonds in molecules

H. Nakai, Y. Kikuchi

J. Theor. Comp. Chem. 4(1) p.317 - 3322005/03-

DOI

Practical performance assessment of accompanying coordinate expansion recurrence relation algorithm for computation of electron repulsion integrals

M. Katouda, M. Kobayashi, H. Nakai

J. Theor. Comp. Chem. 4(1) p.139 - 1492005/03-

DOI

Theoretical study on excitation dynamics of 5-dibenzosuberene and its derivatives

H. Nakai, T. Baba

Journal of Molecular Structure. 735-736p.211 - 2162005/02-

DOI

Isotope effects in the reaction of H+(H2O)2/D+(D2O)2 with acetone/dimethylsulfoxide

Y. Kawai, Y. Okada, S. Yamaguchi, K. Takeuchi, Y. Yamauchi, H. Nakai

J. Mass Spectrom. Soc. Jpn. 53(6) p.305 - 3082005-

DOI

Short-time Fourier transform analysis of ab initio molecular dynamics simulation: case for collision reaction between NH<SUB>4</SUB><SUP>+ </SUP>(NH<SUB>3</SUB>)<SUB>2 </SUB>and NH<SUB>3</SUB>

Y. Yamauchi, H. Nakai, and Y. Okada

121(22) p.11098 - 111032004/12-

DOI

A hybrid approach combining energy density analysis with the interaction energy decomposition method

Y. Kawamura, H. Nakai

J. Comp. Chem. 25(15) p.1882 - 18872004/11-

DOI

Energy density analysis of cluster size dependence of surface-molecule interactions: H<SUB>2</SUB>, C<SUB>2</SUB>H<SUB>2</SUB>C<SUB>2</SUB>H<SUB>4 </SUB>and CO adsorption onto Si(100)-(2×1) surface

H. Nakai, M. Katouda, Y. Kawamura

J. Chem. Phys., 121(10) p.4893 - 49002004/09-

DOI

New recurrence relations for the rapid evaluation of electron repulsion integrals based on accompanying coordinate expansion formula

M. Kobayashi, H. Nakai

J. Chem. Phys., 121(9) p.4050 - 40582004/09-

DOI

Ab initio molecular orbital study of the electron emission mechanism of TiCl3 as a reductant for an electroless deposition process

M. Shimada, I. Komatsu, T. Homma, H. Nakai, T. Osaka

Electrochemistry 72(6) p.462 - 4652004/06-

New algorithm for the rapid evaluation of electron repulsion integrals: elementary basis algorithm

H. Nakai, M. Kobayashi

Chem. Phys. Lett./Elsevier 388(1〜3) p.50 - 542004/04-

DOI

Theoretical study on the excited states of psoralen compounds bonded to a thymine residue

A. Nakata, T. Baba, H. Takahashi, H. Nakai

J. Comp. Chem./John Wiley & Sons 25(2) p.179 - 1882004/01-

DOI

Size-Dependent Reaction Cross Section of Protonated Water Clusters H<SUP>+</SUP>(H<SUB>2</SUB>O)<SUB>n</SUB> (n = 2-11) with D<SUB>2</SUB>O

S. Yamaguchi, S. Kudoh, Y. Okada, T. Orii, K. Takeuchi, T. Ichikawa, H. Nakai

J. Phys. Chem. A. /American Institute of Physics 107(50) p.10904 - 109102003/12-

DOI

Molecular orbital study on the reaction process of dimethylamine borane as a reductant for electroless deposition

T. Homma, A. Tamaki, H. Nakai, T. Osaka

J. Electroanalytical Chem. 559p.131 - 1362003/11-

DOI

Energy density analysis (EDA) of proton transfer reactions in malonaldehyde, tropolone, and 9-hydroxyphenalenone

H. Nakai, K. Sodeyama

J. Mol. Struct. (THEOCHEM) 637(1〜3) p.27 - 352003/10-

DOI

Ab initio molecular dynamics study on the excitation dynamics of psoralen compounds

H. Nakai, Y. Yamauchi, A. Nakata, T. Baba, H. Takahashi

J. Chem. Phys. 119(8) p.4223 - 42282003/08-

DOI

Reactions of protonated water clusters H<SUP>+</SUP>(H<SUB>2</SUB>O)<SUB>n </SUB>(n = 2-6) with dimethylsulfoxide in a guided ion beam apparatus

Y. Kawai, S. Yamaguchi, Y. Okada, K. Takeuchi, Y. Yamauchi, S. Ozawa, H. Nakai

Chem. Phys. Lett. 377(1〜2) p.69 - 732003/08-

DOI

Energy density analysis of internal methyl rotations in halogenated toluenes

Y. Kawamura, H. Nakai

Chem. Phys. Lett. 368(5〜6) p.673 - 6792003/01-

DOI

Many-body effects in nonadiabatic molecular theory for simultaneous determination of nuclear and electronic wave functions: Ab initio NOMO/MBPT and CC methods

H. Nakai, K. Sodeyama

J. Chem. Phys. 118(3) p.1119 - 11272003/01-

DOI

化学ってそういうこと!-夢が広がる分子の世界-

中井浩巳, 日本化学会編(共著)

化学同人 2003-

DFT Calculation Analysis of the Infrared Spectra of Ethylene Adsorbed on Cu(110), Pd(110) and Ag(110)

K. Itoh, T. Kiyohara, H. Shinohara, C. Ohe, Y. Kawamura, H. Nakai

J. Phys. Chem. B. 106(41) p.10714 - 107212002/10-

DOI

Energy density analysis (EDA) of cis, trans-enol isomerization reactions in malonaldehyde, tropolone, and 9-hydroxyphenalenone

H. Nakai, K. Sodeyama

Chem. Phys. Lett. 365(3〜4) p.203 - 2102002/10-

DOI

Ab initio MD simulation of collision reaction between ammonia cluster ion and ammonia monomer

H. Nakai, Y. Yamauchi, A. Matsuda, Y. Okada, K. Takeuchi

J. Mol. Struct. (THEOCHEM) 592(1〜3) p.61 - 672002/09-

DOI

Energy Density Analysis with Kohn-Sham Orbitals

H. Nakai

Chem. Phys. Lett. 363(1〜2) p.73 - 792002/09-

DOI

Simultaneous determination of nuclear and electronic wave functions without Born-Oppenheimer approximation: Ab initio NO+MO/HF theory

H. Nakai

Int. J. Quant. Chem. 86(6) p.511 - 5172002-

DOI

The Stability of Ammonia Cluster Ions and Its Relation to Nucleation Rate

Y. Okada, T. Orii, K. Takeuchi, H. Nakai, T. Ichikawa

J. Aerosol Res. Jpn. 17(1) p.30 - 382002-

π-σ<SUP>*</SUP> Hyperconjugation mechanism on methyl rotation in cationic state of substituted toluenes

M. Kawai, H. Nakai

Chem. Phys. 273(2〜3) p.191 - 1962001/11-

DOI

Molecular orbital study on the reaction mechanisms of electroless deposition processes

T. Homma, I. Komatsu, A. Tamaki, H. Nakai, T. Osaka

Electrochimica Acta. 47(1〜2) p.47 - 532001/09-

DOI

Non Born-Oppenheimer theory for simultaneous determination of vibrational and electronic excited states: Ab initio NO+MO/CIS theory

H. Nakai, K. Sodeyama, M. Hoshino

Chem. Phys. Lett. 345(1〜2) p.118 - 1242001/09-

DOI

π<SUP>*</SUP>-σ<SUP>*</SUP> Hyperconjugation mechanism on the rotational barrier of the methyl group(III):Methyl-azabenzenes in the ground,excited,and anionic states

Y. Kawamura, T. Nagasawa, H. Nakai

J. Chem. Phys. 114(19) p.8357 - 83632001/05-

DOI

Ab Initio Molecular Orbital Study of the Oxidation Mechanism of Hypophosphite Ion as a Reductant for an Electroless Deposition Process

H. Nakai, T. Homma, I. Komatsu

J. Phys. Chem. B. 105(9) p.1701 - 17042001/03-

DOI

Theoretical study on ammonia cluster ions: nature of thermodynamic magic number

H. Nakai, T. Goto, T. Ichikawa

Chem. Phys. 262(2〜3) p.201 - 2102000/12-

DOI

π<SUP>*</SUP>-σ<SUP>*</SUP> Hyperconjugation Mechanism on the Rotational Barrier of the Methyl Group (I): Substituted Toluenes in the Ground,Excited and Anionic States

H. Nakai, M. Kawai

J. Chem. Phys. 113(6) p.2168 - 21742000/08-

DOI

Theoretical study on ammonia cluster ions: nature of kinetic magic number

H. Nakai, T. Goto, Y. Okada, T. Orii, K. Takeuchi, M. Ichihashi, T. Kondow

J. Chem. Phys. 112(17) p.7409 - 74152000/05-

DOI

π<SUP>*</SUP>-σ<SUP>*</SUP> Hyperconjugation Mechanism on the Rotational Barrier of the Methyl Group (II): 1- and 2-Methylnaphthalenes in the S<SUB>0</SUB>, S<SUB>1</SUB>, C<SUB>0</SUB>, and A<SUB>1</SUB> States

H. Nakai, M. Kawai

Chem. Phys. Lett. 318(4〜5) p.298 - 3042000/02-

DOI

Nature of the Change in the Rotational Barrier of the Methyl Group due to S<SUB>0</SUB> > S<SUB>1</SUB> Excitation

H. Nakai, M. Kawai

Chem. Phys. Lett. 307(3〜4) p.272 - 2761999/07-

DOI

Ab Initio Molecular Orbital Study on the Oxidation Mechanism for Dimethylamine Borane as a Reductant for an Electroless Deposition Process

T. Homma, H. Nakai, M. Onishi, T. Osaka

J. Phys. Chem. B. 103(10) p.1774 - 17781999/02-

DOI

An Extension of the Ab Initio Molecular Orbital Theory to the Nuclear Motion

M. Tachikawa, K. Mori, H. Nakai, K. Iguchi

Chem. Phys. Lett. 290(4〜6) p.437 - 4421998/07-

DOI

A Theoretical Study of the Photochemical Reductive Elimination and Thermal Oxidative Addition of Molecular Hydrogen from and to the Ir-Complex

, Y. Hayashi, H. Nakai, Y. Tokita, H. Nakatsuji

Theor. Chem. Acta 99(4) p.210 - 2141998/05-

DOI

Oxidation Mechanism of Propylene on an Ag Surface: Dipped Adcluster Model Study

H. Nakatsuji, Z. Hu, H. Nakai, K. Ikeda

Surf. Sci. 401(3) p.371 - 3911998/04-

DOI

Electronic structures of MoF<SUB>6</SUB> and MoOF<SUB>4</SUB>in the ground and excited states :A SAC-CI and frozen-orbital-analysis study

H. Nakai, H. Morita, P. Tomasello, H. Nakatsuji

J. Phys. Chem. A. 102(11) p.2033 - 20431998/03-

DOI

Theoretical Studies on the Catalytic Activity of Ag Surface for the Oxidation of Olefins

H. Nakatsuji, Z. M. Hu, H. Nakai

Int. J. Quant. Chem. 65(5) p.839 - 8551997/12-

DOI

Activation of O<SUB>2</SUB> on Cu, Ag, and Au Surfaces for the Epoxidation of Ethylene: Dipped Adcluster Model Study

H. Nakatsuji, Z. Hu, H. Nakai, K. Ikeda

Surf. Sci. 387(1〜3) p.328 - 3411997/10-

DOI

Electronic Structures of the Ground and Excited States of Mo(CO)<SUB>6</SUB>: SAC-CI Calculation and Frozen Orbital Analysis

H. Morita, H. Nakai, H. Hanada, H. Nakatsuji

Mol. Phys. 92(3) p.523 - 5341997/10-

DOI

Mechanism of the Partial Oxidation of Ethylene on an Ag Surface: Dipped Adcluster Model Study

H. Nakatsuji, H. Nakai, K. Ikeda, Y. Yamamoto

Surf. Sci. 384(1〜3) p.315 - 3331997/07-

DOI

Theoretical study on the thermal and photochemical isomerization reactions of dicyanoacetylene complex of platinum Pt(PH<SUB>3</SUB>)<SUB>2</SUB>(C<SUB>4</SUB>N<SUB>2</SUB>)

H. Nakai, S. Fukada, H. Nakatsuji

J. Phys. Chem. A. 101(6) p.973 - 9801997/02-

DOI

Ab initio molecular orbital model of scanning tunneling microscopy: Benzene and benzene adsorbed on a Ag surface

M. Hidaka, T. Fujita, H. Nakai, H. Nakatsuji

Chem. Phys. Lett. 264(3〜4) p.371 - 3751997/01-

DOI

Frozen- orbital analysis for the excited states of metal complexes in high symmetry: O <SUB>h</SUB> case

H. Nakai, H. Morita, H. Nakatsuji

J. Phys. Chem. 100(39) p.15753 - 157591996/09-

DOI

Theoretical study of the ionized electronic structure of the octahedral complex MoF<SUB>6</SUB>

H. Morita, H. Nakai, P. Tomasello, H. Nakatsuji

Bull. Chem. Soc. Jpn. 69(7) p.1893 - 18991996/07-

DOI

Ab Initio Molecular Orbital Model of Scanning Tunneling Microscope

T. Fujita, H. Nakai, H. Nakatsuji

J. Chem. Phys. 104(6) p.2410 - 24171996/01-

DOI

CO and NO adsorption on copper-containing zeolite: A theoretical ab initio study

N. U. Zhanpeisov, H. Nakatsuji, M. Hada, H. Nakai

Catal. Lett. 42(3〜4) p.173 - 1761996-

DOI

Theoretical study on the photostimulated desorption of CO from a Pt surface

H. Nakatsuji, H. Morita, H. Nakai, Y. Murata, K. Fukutani

J. Chem. Phys. 104(2) p.714 - 7261996-

DOI

Theoretical study on the electronic spectrum of TcO<SUB>4</SUB><SUP>-</SUP>

J. Hasegawa, K. Toyota, M. Hada, H. Nakai, H. Nakatsuji

Theoret. Chem. Acta. 92(6) p.351 - 3591995/12-

Electronic mechanism of the surface enhanced Raman scattering

H. Nakai, H. Nakatsuji

J. Chem. Phys. 103(6) p.2286 - 22941995/08-

DOI

Theoretical study on the photochemical decomposition reaction of permanganate ion, MnO<SUB>4</SUB><SUP>-</SUP>

H. Nakai, Y. Ohmori, H. Nakatsuji

J. Phys. Chem. 99(21) p.8550 - 85551995/05-

DOI

Mechanism of photochemical reaction of permanganate ion

H. Nakai, H. Nakatsuji

J. Mol. Struct. (THEOCHEM) 311p.141 - 1511994/07-

DOI

Theoretical study on the ground and excited states of the chromate anion CrO<SUB>4</SUB><SUP>2-</SUP>

S. Jitsuhiro, H. Nakai, M. Hada, H. Nakatsuji

J. Chem. Phys. 101(2) p.1029 - 10361994/07-

DOI

「固体触媒作用の量子化学」

中辻博, 波田雅彦, 中井浩巳, 福西快文

触媒 36(1) p.33 - 401994-

「表面光化学反応の理論展開」

中辻博, 中井浩巳

有機合成化学研究所講演集、第8集 p.92 - 1001994-

Dipped adcluster model and SAC-CI method applied to harpooning, chemiluminescence and electronemission in halogen chemisorption on alkali metal surface

H. Nakatsuji, R. Kuwano, H. Morita, H. Nakai

J. Mol. Catal. 82(2〜3) p.211 - 2281993/06-

DOI

Theoretical study on the methane activation reactions by Pt, Pt<SUP>+</SUP>, and Pt<SUP>-</SUP> atoms

M. Hada, H. Nakatsuji, H. Nakai, S. Gyobu, S. Miki

J. Mol. Struct. (THEOCHEM) 281(2〜3) p.207 - 2121993/04-

DOI

Dipped adcluster model study for molecular and dissociative chemisorption of O<SUB>2</SUB> on Ag surface

H. Nakatsuji, H. Nakai

J. Chem. Phys. 98(3) p.2423 - 24361993/02-

DOI

固体表面上での化学吸着と触媒反応の電子論

中辻博, 波田雅彦, 中井浩巳

表面科学 14(10) p.603 - 6091993-

Potential energy curves of dioxygen anion species: O<SUB>2</SUB><SUP>-</SUP>and O<SUB>2</SUB><SUP>2-</SUP>

H. Nakatsuji, H. Nakai

Chem. Phys. Lett. 197(4〜5) p.339 - 3451992/09-

DOI

Dipped adcluster model study for the end-on chemisorption of O<SUB>2</SUB> on an Ag surface

H. Nakatsuji, H. Nakai

Can. J. Chem. 70(2) p.404 - 4081992/02-

Catalytic reactions of transition metal clusters and surfaces from ab initio theory-cluster and dipped adcluster model studies combined with the SAC/SAC-CI method-

H. Nakatsuji, H. Nakai, M. Hada

‘Metal-ligand interctions: from atoms, to clusters, to surfaces’, Ed. D. R. Salahub, NATO ASI Series, Reidel, Dordrecht 1992-

Theoretical study on the ground and excited states of MnO<SUB>4</SUB><SUP>-</SUP>

H. Nakai, Y. Ohmori, H. Nakatsuji

J. Chem. Phys. 95(11) p.8287 - 82911991/12-

DOI

Dipped adcluster model for chemisorptions and catalytic reactions on a metal surface: image force correction and applications to Pd-O<SUB>2</SUB> adclusters

H. Nakatsuji, H. Nakai, Y. Fukunishi

J. Chem. Phys. 95(1) p.640 - 6471991/02-

DOI

金属表面における化学吸着と触媒作用

中井浩巳, 福西快文, 中辻博

季刊化学総説 13p.158 - 1781991-

触媒作用の量子化学

中辻博, 波田雅彦, 中井浩巳

有機合成化学研究所 講演集 5p.59 - 721991-

Theoretical study on molecular and dissociative chemisorptions of an O<SUB>2</SUB> molecule on an Ag surface: dipped adcluster model combined with symmetry adapted cluster-configuration interaction method

H. Nakatsuji, H. Nakai

Chem. Phys. Lett. 174(3〜4) p.283 - 2861990/01-

DOI

Time-dependent Hartree-Fock frequency-dependent polarizability calculation applied to divide-and-conquer electronic structure method

Touma, Tsuguki;Kobayashi, Masato;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 485(1-3) p.247 - 2522010-2010

DOIWoS

Detail

ISSN:0009-2614

Short-time Fourier transform analysis of real-time time-dependent Hartree-Fock and time-dependent density functional theory calculations with Gaussian basis functions

Akama, Tomoko;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 132(5) 2010-2010

DOIWoS

Detail

ISSN:0021-9606

Extension of energy density analysis to periodic-boundary-condition calculations with plane-wave basis functions

Imamura, Yutaka;Takahashi, Asuka;Okada, Takeshi;Ohno, Takahisa;Nakai, Hiromi

PHYSICAL REVIEW B 81(11) 2010-2010

DOIWoS

Detail

ISSN:1098-0121

Acceleration of self-consistent-field convergence in ab initio molecular dynamics and Monte Carlo simulations and geometry optimization

Atsumi, Teruo;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 490(1-3) p.102 - 1082010-2010

DOIWoS

Detail

ISSN:0009-2614

Application of Real-time Time-dependent Density Functional Theory with the CVB3LYP Functional to Core Excitations

Akama, Tomoko;Imamura, Yutaka;Nakai, Hiromi

CHEMISTRY LETTERS 39(4) p.407 - 4092010-2010

DOIWoS

Detail

ISSN:0366-7022

Observation by UV-Visible and NMR Spectroscopy and Theoretical Confirmation of 4-Isopropyltropolonate Ion, 4-Isopropyltropolone (Hinokitiol), and Protonated 4-Isopropyltropolone in Acetonitrile

Hojo, Masashi;Ueda, Tadaharu;Ike, Michitaka;Okamura, Kei;Sugiyama, Taku;Kobayashi, Masato;Nakai, Hiromi

JOURNAL OF CHEMICAL AND ENGINEERING DATA 55(5) p.1986 - 19892010-2010

DOIWoS

Detail

ISSN:0021-9568

Theoretical Study of Bond-Switching in 1,6-Dihydro-6a-thia-1,6-diazapentalene (10-S-3) Systems Compared with Corresponding Oxygen Analogues

Atsumi, Teruo;Abe, Tomohiro;Akiba, Kin-ya;Nakai, Hiromi

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 83(5) p.520 - 5292010-2010

DOIWoS

Detail

ISSN:0009-2673

Generalized Moller-Plesset Partitioning in Multiconfiguration Perturbation Theory

Kobayashi, Masato;Szabados, Agnes;Nakai, Hiromi;Surjan, Peter R.

JOURNAL OF CHEMICAL THEORY AND COMPUTATION 6(7) p.2024 - 20332010-2010

DOIWoS

Detail

ISSN:1549-9618

Theoretical Study of Hypervalent Bonds in 1,6-Diaza-1,6-dihydro- and 1,6-Dihydro-1,6-dioxapentalene Systems with a Heteroatom X at 6a Position (X=14-16 Group Atoms)

Atsumi, Teruo;Abe, Tomohiro;Akiba, Kin-ya;Nakai, Hiromi

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 83(8) p.892 - 8992010-2010

DOIWoS

Detail

ISSN:0009-2673

Unusual Energy Balance Between Atoms in Postperovskite MgSiO3

Hirate, Hiroshi;Sawai, Hiroshi;Saito, Yuki;Yukawa, Hiroshi;Morinaga, Masahiko;Nakai, Hiromi

JOURNAL OF THE AMERICAN CERAMIC SOCIETY 93(10) p.3449 - 34542010-2010

DOIWoS

Detail

ISSN:0002-7820

Divide-and-conquer self-consistent field calculation for open-shell systems: Implementation and application

Kobayashi, Masato;Yoshikawa, Takeshi;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 500(1-3) p.172 - 1772010-2010

DOIWoS

Detail

ISSN:0009-2614

Local response dispersion method. II. Generalized multicenter interactions

Sato, Takeshi;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 133(19) 2010-2010

DOIWoS

Detail

ISSN:0021-9606

Reconsidering an analytical gradient expression within a divide-and-conquer self-consistent field approach: Exact formula and its approximate treatment

Kobayashi, Masato;Kunisada, Tomotaka;Akama, Tomoko;Sakura, Daisuke;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 134(3) 2011-2011

DOIWoS

Detail

ISSN:0021-9606

Quantitative Evaluation of Catalytic Effect of Metal Chlorides on the Decomposition Reaction of NaAlH4

Hirate, Hiroshi;Saito, Yuki;Nakaya, Ippei;Sawai, Hiroshi;Yukawa, Hiroshi;Morinaga, Masahiko;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 111(5) p.950 - 9602011-2011

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ISSN:0020-7608

Interpretation of Intermolecular Geometric Isotope Effect in Hydrogen Bonds: Nuclear Orbital plus Molecular Orbital Study

Ikabata, Yasuhiro;Imamura, Yutaka;Nakai, Hiromi

JOURNAL OF PHYSICAL CHEMISTRY A 115(8) p.1433 - 14392011-2011

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ISSN:1089-5639

Linearity condition for orbital energies in density functional theory: Construction of orbital-specific hybrid functional

Imamura, Yutaka;Kobayashi, Rie;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 134(12) 2011-2011

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ISSN:0021-9606

Energy expression of the chemical bond between atoms in metal oxides

Shinzato, Yoshifumi;Saito, Yuki;Yoshino, Masahito;Yukawa, Hiroshi;Morinaga, Masahiko;Baba, Takeshi;Nakai, Hiromi

JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS 72(7) p.853 - 8612011-2011

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ISSN:0022-3697

Development of linear-scaling electronic-structure calculation based on divide-and-conquer approach

Nakai, Hiromi

ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 2412011-2011

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ISSN:0065-7727

Theoretical Design of Hexacoordinate Hypervalent Carbon Compounds by Analyzing Substituent Effects

Nakai, Hiromi;Okoshi, Masaki;Atsumi, Teruo;Kikuchi, Yasuaki;Akiba, Kin-ya

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 84(5) p.505 - 5102011-2011

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ISSN:0009-2673

Rigorous non-Born-Oppenheimer theory: Combination of explicitly correlated Gaussian method and nuclear orbital plus molecular orbital theory

Hoshino, Minoru;Nishizawa, Hiroaki;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 135(2) 2011-2011

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ISSN:0021-9606

Density Functional Theory Analysis of Reaction Mechanism of Hypophosphite Ions on Metal Surfaces

Kunimoto, Masahiro;Shimada, Takuya;Odagiri, Shuichi;Nakai, Hiromi;Homma, Takayuki

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 158(9) p.D585 - D5892011-2011

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ISSN:0013-4651

Density Functional Theory Analysis for Orbital Interaction between Hypophosphite Ions and Metal Surfaces

Kunimoto, Masahiro;Nakai, Hiromi;Homma, Takayuki

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 158(10) p.D626 - D6332011-2011

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ISSN:0013-4651

Two-Level Hierarchical Parallelization of Second-Order Moller-Plesset Perturbation Calculations in Divide-and-Conquer Method

Katouda, Michio;Kobayashi, Masato;Nakai, Hiromi;Nagase, Shigeru

JOURNAL OF COMPUTATIONAL CHEMISTRY 32(13) p.2756 - 27642011-2011

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ISSN:0192-8651

Linearity condition for orbital energies in density functional theory (II): Application to global hybrid functionals

Imamura, Yutaka;Kobayashi, Rie;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 513(1-3) p.130 - 1352011-2011

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ISSN:0009-2614

Bond energy analysis revisited and designed toward a rigorous methodology

Nakai, Hiromi;Ohashi, Hideaki;Imamura, Yutaka;Kikuchi, Yasuaki

JOURNAL OF CHEMICAL PHYSICS 135(12) 2011-2011

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ISSN:0021-9606

Linear-scaling divide-and-conquer second-order Moller-Plesset perturbation calculation for open-shell systems: implementation and application

Yoshikawa, Takeshi;Kobayashi, Masato;Nakai, Hiromi

THEORETICAL CHEMISTRY ACCOUNTS 130(2-3) p.411 - 4172011-2011

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ISSN:1432-881X

Finite-field evaluation of static (hyper)polarizabilities based on the linear-scaling divide-and-conquer method

Touma, Tsuguki;Kobayashi, Masato;Nakai, Hiromi

THEORETICAL CHEMISTRY ACCOUNTS 130(4-6) p.701 - 7092011-2011

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ISSN:1432-881X

Evaluation of electron repulsion integral of the explicitly correlated Gaussian-nuclear orbital plus molecular orbital theory

Nishizawa, Hiroaki;Hoshino, Minoru;Imamura, Yutaka;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 521p.142 - 1492012-2012

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ISSN:0009-2614

Dynamic hyperpolarizability calculations of large systems: The linear-scaling divide-and-conquer approach

Kobayashi, Masato;Touma, Tsuguki;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 136(8) 2012-2012

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ISSN:0021-9606

Constrained self-consistent field method revisited toward theoretical designs of functional materials under external field

Yamagata, Yuya;Imamura, Yutaka;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 530p.132 - 1362012-2012

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ISSN:0009-2614

Theoretical Analysis of Catalytic Activity of Metal Surfaces on Reaction of Hypophosphite Ion

Kunimoto, Masahiro;Nakai, Hiromi;Homma, Takayuki

ELECTROCHEMISTRY 80(3) p.126 - 1312012-2012

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ISSN:1344-3542

Development of the explicitly correlated Gaussian-nuclear orbital plus molecular orbital theory: Incorporation of electron-electron correlation

Nishizawa, Hiroaki;Imamura, Yutaka;Ikabata, Yasuhiro;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 533p.100 - 1052012-2012

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ISSN:0009-2614

Theoretical Analysis of Adsorption Structure of Hydrated Hypophosphite Ion on Pd (111) Surface

Kunimoto, Masahiro;Seki, Kenji;Nakai, Hiromi;Homma, Takayuki

ELECTROCHEMISTRY 80(4) p.222 - 2252012-2012

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ISSN:1344-3542

How does it become possible to treat delocalized and/or open-shell systems in fragmentation-based linear-scaling electronic structure calculations? The case of the divide-and-conquer method

Kobayashi, Masato;Nakai, Hiromi

PHYSICAL CHEMISTRY CHEMICAL PHYSICS 14(21) p.7629 - 76392012-2012

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ISSN:1463-9076

Local unitary transformation method for large-scale two-component relativistic calculations: Case for a one-electron Dirac Hamiltonian

Seino, Junji;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 136(24) 2012-2012

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ISSN:0021-9606

Direct alkoxysilylation of alkoxysilanes for the synthesis of explicit alkoxysiloxane oligomers

Wakabayashi, Ryutaro;Tamai, Misa;Kawahara, Kazufumi;Tachibana, Hiroki;Imamura, Yutaka;Nakai, Hiromi;Kuroda, Kazuyuki

JOURNAL OF ORGANOMETALLIC CHEMISTRY 716p.26 - 312012-2012

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ISSN:0022-328X

Extension of local response dispersion method to excited-state calculation based on time-dependent density functional theory

Ikabata, Yasuhiro;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 137(12) 2012-2012

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ISSN:0021-9606

Local unitary transformation method for large-scale two-component relativistic calculations. II. Extension to two-electron Coulomb interaction

Seino, Junji;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 137(14) 2012-2012

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ISSN:0021-9606

Generalized Moller-Plesset Multiconfiguration Perturbation Theory Applied to an Open-Shell Antisymmetric Product of Strongly Orthogonal Geminals Reference Wave Function

Tarumi, Moto;Kobayashi, Masato;Nakai, Hiromi

JOURNAL OF CHEMICAL THEORY AND COMPUTATION 8(11) p.4330 - 43352012-2012

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ISSN:1549-9618

Cristaxenicin A, an Antiprotozoal Xenicane Diterpenoid from the Deep Sea Gorgonian Acanthoprimnoa cristata

Ishigami, Shin-Taro;Goto, Yasuyuki;Inoue, Noboru;Kawazu, Shin-Ichiro;Matsumoto, Yoshitsugu;Imahara, Yukimitsu;Tarumi, Moto;Nakai, Hiromi;Fusetani, Nobuhiro;Nakao, Yoichi

JOURNAL OF ORGANIC CHEMISTRY 77(23) p.10962 - 109662012-2012

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ISSN:0022-3263

Divide-and-conquer-based symmetry adapted cluster method: Synergistic effect of subsystem fragmentation and configuration selection

Yoshikawa, Takeshi;Kobayashi, Masato;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 113(3) p.218 - 2232013-2013

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ISSN:0020-7608

Accelerating convergence in the antisymmetric product of strongly orthogonal geminals method

Tarumi, Moto;Kobayashi, Masato;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 113(3) p.239 - 2442013-2013

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ISSN:0020-7608

Linearity condition for orbital energies in density functional theory (IV): Determination of range-determining parameter

Imamura, Yutaka;Kobayashi, Rie;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 113(3) p.245 - 2512013-2013

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ISSN:0020-7608

Self-consistent field treatment and analytical energy gradient of local response dispersion method

Ikabata, Yasuhiro;Sato, Takeshi;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 113(3) p.257 - 2622013-2013

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ISSN:0020-7608

Assessment of local response dispersion method for open-shell systems

Ikabata, Yasuhiro;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 556p.386 - 3922013-2013

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ISSN:0009-2614

Divide-and-conquer-based quantum chemical study for interaction between HIV-1 reverse transcriptase and MK-4965 inhibitor

Saparpakorn, Patchreenart;Kobayashi, Masato;Hannongbua, Supa;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 113(4) p.510 - 5172013-2013

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ISSN:0020-7608

An effective energy gradient expression for divide-and-conquer second-order Moller-Plesset perturbation theory

Kobayashi, Masato;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 138(4) 2013-2013

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ISSN:0021-9606

Divide-and-Conquer Electronic-Structure Study on the Mechanism of the West Nile Virus NS3 Protease Inhibitor

Saparpakorn, Patchreenart;Kobayashi, Masato;Nakai, Hiromi

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 86(1) p.67 - 742013-2013

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ISSN:0009-2673

Linearity condition for orbital energies in density functional theory (III): Benchmark of total energies

Imamura, Yutaka;Kobayashi, Rie;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 34(14) p.1218 - 12252013-2013

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ISSN:0192-8651

Novel Approach to Excited-State Calculations of Large Molecules Based on Divide-and-Conquer Method: Application to Photoactive Yellow Protein

Yoshikawa, Takeshi;Kobayashi, Masato;Fujii, Atsuhiko;Nakai, Hiromi

JOURNAL OF PHYSICAL CHEMISTRY B 117(18) p.5565 - 55732013-2013

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ISSN:1520-6106

Acceleration effect of thiourea on the oxidation reaction of hypophosphite ion on Ni surface

Kunimoto, Masahiro;Endo, Kazuaki;Nakai, Hiromi;Homma, Takayuki

ELECTROCHIMICA ACTA 100p.311 - 3162013-2013

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ISSN:0013-4686

Local unitary transformation method toward practical electron correlation calculations with scalar relativistic effect in large-scale molecules

Seino, Junji;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 139(3) 2013-2013

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ISSN:0021-9606

Theoretical Study on Stability of Lithium Ion Battery in Charging Process: Analysis Based on Partial Charge and Partial Energy

Yamauchi, Yusuke;Nakai, Hiromi

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 160(9) p.A1364 - A13682013-2013

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ISSN:0013-4651

Kinetic Energy Decomposition Scheme Based on Information Theory

Imamura, Yutaka;Suzuki, Jun;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 34(32) p.2787 - 27952013-2013

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ISSN:0192-8651

Theoretical Analysis on De-Solvation of Lithium, Sodium, and Magnesium Cations to Organic Electrolyte Solvents

Okoshi, Masaki;Yamada, Yuki;Yamada, Atsuo;Nakai, Hiromi

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 160(11) p.A2160 - A21652013-2013

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ISSN:0013-4651

Superphenalenyl: Theoretical Design of a pi-Conjugated Planar Hydrocarbon Radical

Ikabata, Yasuhiro;Akiba, Kin-ya;Nakai, Hiromi

CHEMISTRY LETTERS 42(11) p.1386 - 13872013-2013

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ISSN:0366-7022

Analytical energy gradient based on spin-free infinite-order Douglas-Kroll-Hess method with local unitary transformation

Nakajima, Yuya;Seino, Junji;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 139(24) 2013-2013

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ISSN:0021-9606

Improving quasiparticle second order electron propagator calculations with the spin-component-scaled technique

Romero, Jonathan;Charry, Jorge A.;Nakai, Hiromi;Reyes, Andres

CHEMICAL PHYSICS LETTERS 591p.82 - 872014-2014

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ISSN:0009-2614

Frozen core potential scheme with a relativistic electronic Hamiltonian: Theoretical connection between the model potential and all-electron treatments

Seino, Junji;Tarumi, Moto;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 592p.341 - 3482014-2014

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ISSN:0009-2614

Theoretical analysis of the influence of surface defects on the reactivity of hypophosphite ions

Kunimoto, Masahiro;Otomo, Akira;Takahashi, Nana;Nakai, Hiromi;Homma, Takayuki

ELECTROCHIMICA ACTA 113p.785 - 7912013-2013

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ISSN:0013-4686

Theoretical Study on the Selective Fluorescence of PicoGreen: Binding Models and Photophysical Properties

Okoshi, Masaki;Saparpakorn, Patchreenart;Takada, Yuta;Hannongbua, Supa;Nakai, Hiromi

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 87(2) p.267 - 2732014-2014

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ISSN:0009-2673

Acceleration of Self-Consistent Field Convergence in Ab Initio Molecular Dynamics Simulation with Multiconfigurational Wave Function

Okoshi, Masaki;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 35(20) p.1473 - 14802014-2014

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ISSN:0192-8651

Extension of Accompanying Coordinate Expansion and Recurrence Relation Method for General-Contraction Basis Sets

Hayami, Masao;Seino, Junji;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 35(20) p.1517 - 15272014-2014

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ISSN:0192-8651

Quantum chemical approach for condensed-phase thermochemistry: Proposal of a harmonic solvation model

Nakai, Hiromi;Ishikawa, Atsushi

JOURNAL OF CHEMICAL PHYSICS 141(17) 2014-2014

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ISSN:0021-9606

Linearity condition for orbital energies in density functional theory (V): Extension to excited state calculations

Imamura, Yutaka;Suzuki, Kensei;Iizuka, Takeshi;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 618p.30 - 362015-2015

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ISSN:0009-2614

Linear-Scaling Self-Consistent Field Calculations Based on Divide-and-Conquer Method Using Resolution-of-Identity Approximation on Graphical Processing Units

Yoshikawa, Takeshi;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 36(3) p.164 - 1702015-2015

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ISSN:0192-8651

Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

Cho, Daeheum;Ko, Kyoung Chul;Ikabata, Yasuhiro;Wakayama, Kazufumi;Yoshikawa, Takeshi;Nakai, Hiromi;Lee, Jin Yong

JOURNAL OF CHEMICAL PHYSICS 142(2) 2015-2015

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ISSN:0021-9606

Large-Scale Two-Component Relativistic Quantum-Chemical Theory: Combination of the Infinite-Order Douglas-Kroll-Hess Method with the Local Unitary Transformation Scheme and the Divide-and-Conquer Method

Seino, Junji;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 115(5) p.253 - 2572015-2015

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ISSN:0020-7608

Local Response Dispersion Method: A Density-Dependent Dispersion Correction for Density Functional Theory

Ikabata, Yasuhiro;Nakai, Hiromi

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 115(5) p.309 - 3242015-2015

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ISSN:0020-7608

Quantum Chemistry beyond Born-Oppenheimer Approximation on a Quantum Computer: A Simulated Phase Estimation Study

Veis, Libor;Visnak, Jakub;Nishizawa, Hiroaki;Nakai, Hiromi;Pittner, Jiri

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 116(18) p.1328 - 13362016-2016

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ISSN:0020-7608

Informatics-Based Energy Fitting Scheme for Correlation Energy at Complete Basis Set Limit

Seino, Junji;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 37(25) p.2304 - 23152016-2016

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ISSN:0192-8651

The divide-and-conquer second-order proton propagator method based on nuclear orbital plus molecular orbital theory for the efficient computation of proton binding energies

Tsukamoto, Yusuke;Ikabata, Yasuhiro;Romero, Jonathan;Reyes, Andres;Nakai, Hiromi

PHYSICAL CHEMISTRY CHEMICAL PHYSICS 18(39) p.27422 - 274312016-2016

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ISSN:1463-9076

Relativistic frozen core potential scheme with relaxation of core electrons

Nakajima, Yuya;Seino, Junji;Hayami, Masao;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 663p.97 - 1032016-2016

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ISSN:0009-2614

Recent Advances in Divide-and-Conquer Density-Functional Tight-Binding Molecular Dynamics Simulations (DC-DFTB-MD)

NISHIMURA Yoshifumi;KAIHO Takeaki;NAKAI Hiromi

Journal of Chemical Software 14(3) p.43 - 462015-2015

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ISSN:1347-1767

Outline:The authors group has developed the program named DC-DFTB-K for the on-the-fly quantum mechanical molecular dynamics (MD) simulation of huge systems using the density-functional tight binding (DFTB) method. The combination with the divide-and-conquer (DC) method enables linear-scaling calculation of DFTB energy and its derivatives. Due to the massively parallel implementation, the program can treat systems containing one million atoms on the K computer. In this paper, the recent extension of DC-DFTB-MD technique is outlined together with the illustrative application to chemical reaction dynamics in lithium-ion device.

Theoretical Study of Extremely Long yet Stable Carbon–Carbon Bonds: Effect of Attractive C···H Interactions and Small Radical Stabilization of Diamondoids

Cho Daeheum;Ikabata Yasuhiro;Yoshikawa Takeshi;Lee Jin Yong;Nakai Hiromi

Bull. Chem. Soc. Jpn. 88(12) p.1636 - 16412015-2015

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ISSN:0009-2673

Outline:The origin of the stability of diamondoid dimers containing very long carbon–carbon bonds was examined using density functional theory (DFT) calculations with local response dispersion correction. It has been suggested that noncovalent CH···HC contacts are the probable source of their extraordinary stability as evidenced by dispersion-corrected DFT calculations. In this work, we numerically proved that the small radical stabilization energy, which was achieved through the geometric relaxation of cleaved radicals, led to the high stability of diamondoid dimers compared to other hydrocarbons. The bond energy density analysis showed that the CH···HC contacts are repulsive though the dispersion force somewhat stabilizes the dimer. We further decomposed CH···HC interaction energies to discover strong attractive interaction between Cδ−···Hδ+ intermonomer contacts.

Electronic Transition Process of Fluorescence Appearing in Various Organic Polymers

Nishikawa Seiya;Tonoi Masashi;Yoshikawa Takeshi;Hirai Naoshi;Nakai Hiromi;Ohki Yoshimichi

The transactions of the Institute of Electrical Engineers of Japan.A 136(4) p.205 - 2112016-2016

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ISSN:0385-4205

Outline:Low density polyethylene (LDPE) and polypropylene (PP) exhibit a photoluminescence (PL) band, which emits photons with an energy of around 4.3 eV when excited by photons with energies around 6.4 eV. The origin of this PL band has been assigned to α, β-unsaturated carbonyl. In this paper, the appearance of PL was examined for four kinds of polyolefin and four kinds of biodegradable polymers. As a result, it has become clear that all the polymers show a PL band with a PL excitation spectrum and a PL spectrum similar to those of the above-mentioned PL band in LDPE and PP. The decay profiles observed for these PL bands indicate that they are fluorescence. Furthermore, the intensity of the PL becomes weak for all the four polyolefin samples and the polylatic acid sample if ultraviolet photons were irradiated to the sample. Quantum chemical calculations carried out by assuming a model of α, β-unsaturated carbonyl have revealed that the PL originates in the π* to π transition of electrons in the carbon-carbon double bond.

Estimation of complete basis set limit in electron correlation energy utilizing informatics technique

Seino Junji;Okoshi Masaki;Nakai Hiromi

Proceedings of the Symposium on Chemoinformatics 2015(0) p.24 - 252015-2015

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Outline:To realize quantum-chemical calculations with chemical accuracy (> 1 kcal/mol), efficient estimations of accurate electron correlation energies in a complete basis set (CBS) limit are important. Several extrapolation schemes to CBS limit, and composite schemes in combination with energies calculated with some levels of theories and basis sets have been proposed. This study proposes efficient estimation schemes of electron correlation energies in a CBS limit at the CCSD(T) level utilizing informatics technique.

Development of Reaction Prediction Scheme Based on Machine Learning with Quantum Chemical Descriptors

FUJINAMI Mikito;SEINO Junji;NAKAI Hiromi

Journal of Computer Chemistry, Japan 15(3) p.63 - 652016-2016

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We have developed a novel reaction prediction system, which uses machine learning with quantum chemical descriptors. Numerical assessments of the system were performed on basic polar and radical organic chemical reactions. The accuracy of the present system was close to that of a previous system having machine learning with topological information, which is termed ReactionPredictor.

Computational Chemistry Studies on CO2 Chemical Absorption Technique: Challenge on Energy and Environmental Issue

TERANISHI Kei;ISHIKAWA Atsushi;NAKAI Hiromi

Journal of Computer Chemistry, Japan 15(2) p.A15 - A292016-2016

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Chemical absorption of CO2 employing alkanolamines is currently considered to be the most promising approach for CO2 emission reduction from power plants. Extensive efforts have been devoted by experimental and theoretical researchers in the development of amine solutions, with the main purpose of reducing the energy cost of solvent regeneration. In the present Commentary, we show how theoretical calculations have been utilized in the analysis of the amine-CO2 reaction mechanism. Theoretical studies with quantum chemistry calculations and ab initio molecular dynamics are mainly focused on.

Development of reaction prediction system based on informatics and quantum chemical calculation

Fujinami Mikito;Seino Junji;Nakai Hiromi

Proceedings of the Symposium on Chemoinformatics 2016(0) 2016-2016

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Outline:In the field of chemoinformatics, computer-aided reaction prediction systems have been developed. However, the systems have not been widely used by experimental chemists because of its low accuracy for predicting chemical reactions. Recently, a reaction prediction scheme, which is based on the machine learning method and utilizes topological information of molecules as descriptors, has shown high effectiveness for organic reactions. Nevertheless, the application has been limited due to lack of steric and electronic information of molecules. The present study has developed a novel scheme, which uses the machine learning with descriptors obtained from quantum chemical calculation, in order to realize an accurate prediction for reactions including arbitrary chemical species such as organometallic and ionic reactions. The accuracy of present system has been clarified to be close to that of the previous system for basic polar and radical organic chemical reactions. In this presentation, we will show the details of the system and the dependencies on conditions of quantum chemical calculations.

Amine-CO2 reaction simulator using quantum chemical calculation and swarm intelligence

Nagato Sumika;Teranishi Kei;Seino Junji;Nakai Hiromi

Proceedings of the Symposium on Chemoinformatics 2016(0) 2016-2016

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Outline:The carbon dioxide capture and storage (CCS), which is a technique to reduce an amount of emission of CO2, has many attentions. The chemical absorption method, which is one scheme of the CCS technique, consists of two processes: a separation process for absorbing CO2 in a basic absorbent and a collection process for emitting high concentrate CO2 by high temperature. Many amines have been studied and developed to reduce the energy in the CO2 absorption. To explore an amine with a high efficiency in the CO2 absorption, the time courses in concentrations of chemical species for each amine give important information. In this study, we develop a reaction predictor to reproduce the experimental data, which uses elementary processes in a CO2
-amine reaction and the swarm intelligence. Furthermore, equilibrium constants for elementary processes are estimated from reaction Gibbs energies obtained by quantum chemical calculations in order to predict loading dependencies of chemical species in any amines.

Implementation of Efficient Two-component Relativistic Method Using Local Unitary Transformation to GAMESS Program

NAKAJIMA Yuya;SEINO Junji;SCHMIDT Michael W.;NAKAI Hiromi

Journal of Computer Chemistry, Japan 15(3) p.68 - 702016-2016

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This Letter provides an implementation of an efficient and accurate relativistic method based on the infinite-order two-component scheme with the local unitary transformation (LUT-IOTC) to the GAMESS program. The sample input and major capabilities in GAMESS are shown as well as the accuracies and efficiencies in energy and analytical energy gradient calculations. The scheme realizes calculations of molecules containing heavy elements with four-component relativistic accuracy and the non-relativistic computational cost.

Decomposition of Effective Exchange Integrals of Radical Dimers Using Bond Energy Density Analysis

Ikabata Yasuhiro;Nakai Hiromi

Chemistry Letters 46(6) p.879 - 8822017-2017

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In this letter, effective exchange integrals of radical dimers obtained by density functional calculations are decomposed into atomic-pair components. The bond energy density analysis, which was originally proposed to evaluate the energy of a chemical bond, was found to be a useful tool to analyze the magnetic interaction of radical dimers.

Harmonic Solvation Model (HSM) for Evaluation of Condensed-Phase Free Energy

NAKAI Hiromi

Journal of Computer Chemistry, Japan 16(4) p.83 - 882017-2017

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We have proposed a novel quantum chemical model to evaluate condensed-phase thermodynamic properties, that is, the harmonic solvation model (HSM). This paper explains the theoretical background of HSM and the practical procedure to use for the HSM with some sample inputs. Illustrative applications demonstrate the usefulness and accuracy of HSM.

Short-time Fourier transform analysis of real-time time-dependent Hartree-Fock and time-dependent density functional theory calculations with Gaussian basis functions.

Akama Tomoko;Nakai Hiromi

Short-time Fourier transform analysis of real-time time-dependent Hartree-Fock and time-dependent density functional theory calculations with Gaussian basis functions. 132(5) 2010-2010

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ISSN:1089-7690

Outline::We propose a novel analysis of real-time (RT) time-dependent Hartree-Fock and time-dependent density functional theory (TDHF/TDDFT) calculations using a short-time Fourier transform (STFT) technique. RT-TDHF/TDDFT calculations of model dimers were carried out and analyzed using the STFT technique, in addition to the usual Fourier transform (FT). STFT analysis revealed that the induced polarization propagated between the molecules through the intermolecular interaction; that is, it directly showed the electron dynamics of the excited system. The dependence of the propagation period on the intermolecular distance of the dimer was investigated. We also proved the possibility of describing, not just the valence, but also the core excitations by FT analysis of the RT-TDHF/TDDFT calculations of a formaldehyde monomer with Gaussian basis functions compared with conventional TDHF/TDDFT results.

Local response dispersion method. II. Generalized multicenter interactions.

Sato Takeshi;Nakai Hiromi

Local response dispersion method. II. Generalized multicenter interactions. 133(19) 2010-2010

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ISSN:1089-7690

Outline::Recently introduced local response dispersion method [T. Sato and H. Nakai, J. Chem. Phys. 131, 224104 (2009)], which is a first-principles alternative to empirical dispersion corrections in density functional theory, is implemented with generalized multicenter interactions involving both atomic and atomic pair polarizabilities. The generalization improves the asymptote of intermolecular interactions, reducing the mean absolute percentage error from about 30% to 6% in the molecular C(6) coefficients of more than 1000 dimers, compared to experimental values. The method is also applied to calculations of potential energy curves of molecules in the S22 database [P. Jurečka et al., Phys. Chem. Chem. Phys. 8, 1985 (2006)]. The calculated potential energy curves are in a good agreement with reliable benchmarks recently published by Molnar et al. [J. Chem. Phys. 131, 065102 (2009)]. These improvements are achieved at the price of increasing complexity in the implementation, but without losing the computational efficiency of the previous two-center (atom-atom) formulation. A set of different truncations of two-center and three- or four-center interactions is shown to be optimal in the cost-performance balance.

Reconsidering an analytical gradient expression within a divide-and-conquer self-consistent field approach: exact formula and its approximate treatment.

Kobayashi Masato;Kunisada Tomotaka;Akama Tomoko;Sakura Daisuke;Nakai Hiromi

Reconsidering an analytical gradient expression within a divide-and-conquer self-consistent field approach: exact formula and its approximate treatment. 134(3) 2011-2011

DOI

Detail

ISSN:1089-7690

Outline::An analytical energy gradient formula for the density-matrix-based linear-scaling divide-and-conquer (DC) self-consistent field (SCF) method was proposed in a previous paper by Yang and Lee (YL) [J. Chem. Phys. 103, 5674 (1995)]. Since the formula by YL does not correspond to the exact gradient of the DC-SCF energy, we derive the exact formula by direct differentiation, which requires solving the coupled-perturbed equations while including the inter-subsystem coupling terms. Next, we present an alternative formula for approximately evaluating the DC-SCF energy gradient, assuming the variational condition for the subsystem density matrices. Numerical assessments confirmed that the DC-SCF energy gradient values obtained by the present formula are in reasonable agreement with the conventional SCF values when adopting a reliable buffer region. Furthermore, the performance of the present method was found to be better than that of the YL method.

Interpretation of intermolecular geometric isotope effect in hydrogen bonds: nuclear orbital plus molecular orbital study.

Ikabata Yasuhiro;Imamura Yutaka;Nakai Hiromi

The journal of physical chemistry. A 115(8) 2011-2011

PubMedDOI

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ISSN:1520-5215

Outline::The intermolecular geometric isotope effect (GIE) in hydrogen bond A-X···B (X = H and D) is investigated theoretically using the nuclear orbital plus molecular orbital (NOMO) theory. To interpret the GIE in terms of physically meaningful energy components such as electrostatic and exchange-repulsion interactions, the reduced variational space self-consistent-field method is extended to the NOMO scheme. The intermolecular GIE is analyzed as a two-stage process: the intramolecular bond shrinkage and the intermolecular bond elongation. According to the isotopic shifts of energy components described by the NOMO/MP2 method, the intermolecular GIE is approximately interpreted as a process reducing the exchange-repulsion interaction after the decrease of electrostatic interaction.

Linearity condition for orbital energies in density functional theory: construction of orbital-specific hybrid functional.

Imamura Yutaka;Kobayashi Rie;Nakai Hiromi

Linearity condition for orbital energies in density functional theory: construction of orbital-specific hybrid functional. 134(12) 2011-2011

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Detail

ISSN:1089-7690

Outline::This study proposes a novel approach to construct the orbital-specific (OS) hybrid exchange-correlation functional by imposing the linearity condition: ∂(2)E/∂f(i)(2)|(0≤f(i)≤1) = ∂ɛ(i)/∂f(i)|(0≤f(i)≤1) = 0, where E, ε(i), and f(i) represent the total energy, orbital energy, and occupation number of the ith orbital. The OS hybrid exchange-correlation functional, of which the OS Hartree-Fock exchange (HFx) portion is determined by the linearity condition, reasonably reproduces the ionization potentials not only from valence orbitals but also from core ones in a sense of Koopmans' theorem. The obtained short-range HFx portions are consistent with the parameters empirically determined in core-valence-Rydberg-Becke-3-parameter-Lee-Yang-Parr hybrid functional [Nakata et al., J. Chem. Phys., 124, 094105 (2006); ibid, 125, 064109 (2006)].

Bond energy analysis revisited and designed toward a rigorous methodology.

Nakai Hiromi;Ohashi Hideaki;Imamura Yutaka;Kikuchi Yasuaki

Bond energy analysis revisited and designed toward a rigorous methodology. 135(12) 2011-2011

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Detail

ISSN:1089-7690

Outline::The present study theoretically revisits and numerically assesses two-body energy decomposition schemes including a newly proposed one. The new decomposition scheme is designed to make the equilibrium bond distance equivalent with the minimum point of bond energies. Although the other decomposition schemes generally predict the wrong order of the C-C bond strengths of C(2)H(2), C(2)H(4), and C(2)H(6), the new decomposition scheme is capable of reproducing the C-C bond strengths. Numerical assessment on a training set of molecules demonstrates that the present scheme exhibits a stronger correlation with bond dissociation energies than the other decomposition schemes do, which suggests that the new decomposition scheme is a reliable and powerful analysis methodology.

Dynamic hyperpolarizability calculations of large systems: the linear-scaling divide-and-conquer approach.

Kobayashi Masato;Touma Tsuguki;Nakai Hiromi

Dynamic hyperpolarizability calculations of large systems: the linear-scaling divide-and-conquer approach. 136(8) 2012-2012

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Detail

ISSN:1089-7690

Outline::We report a linear-scaling computation method for evaluating the dynamic first hyperpolarizability β based on the divide-and-conquer (DC) method. In the present scheme, we utilized the quasi-density-matrix expression derived from Wigner's (2n + 1) rule for β, where the quasi-density matrices are constructed from the solution obtained via the DC time-dependent self-consistent field (TD-SCF) method [T. Touma, M. Kobayashi, and H. Nakai, Chem. Phys. Lett. 485, 247 (2010)]. Numerical evaluation of π-conjugated and saturated organic chain systems verified that the present scheme considerably reduces the computational time for the β evaluation with a slight loss of accuracy, even around the singular frequency appearing at the electronic excitation energy. This evaluation indicates that the present linear-scaling TD-SCF scheme can also be used to estimate the molecular excitation energy. Furthermore, we succeeded in accurately evaluating the macroscopic second-harmonic generation coefficient of the polyvinylidene fluoride from the molecular (hyper)polarizabilities.

How does it become possible to treat delocalized and/or open-shell systems in fragmentation-based linear-scaling electronic structure calculations? The case of the divide-and-conquer method.

Kobayashi Masato;Nakai Hiromi

How does it become possible to treat delocalized and/or open-shell systems in fragmentation-based linear-scaling electronic structure calculations? The case of the divide-and-conquer method. 14(21) 2012-2012

DOI

Detail

ISSN:1463-9084

Outline::The authors have developed a fragmentation-based linear-scaling electronic structure calculation strategy named the divide-and-conquer (DC) method, which has been implemented into the Gamess program package. Although there are many sorts of fragmentation-based linear-scaling schemes, most of them require the charge and spin multiplicity of each fragment a priori. Therefore, their applications to delocalized and/or open-shell systems have been limited. However, the DC method is a notable exception because the distribution of electrons in the entire system is automatically determined by the universal Fermi level. In this perspective, the authors have summarized the performance of the linear-scaling self-consistent field (SCF) and post-SCF calculations of delocalized and/or open-shell systems based on the DC method. Furthermore, some future prospects of the method have been discussed.

Local unitary transformation method for large-scale two-component relativistic calculations: case for a one-electron Dirac Hamiltonian.

Seino Junji;Nakai Hiromi

Local unitary transformation method for large-scale two-component relativistic calculations: case for a one-electron Dirac Hamiltonian. 136(24) 2012-2012

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Detail

ISSN:1089-7690

Outline::An accurate and efficient scheme for two-component relativistic calculations at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level is presented. The present scheme, termed local unitary transformation (LUT), is based on the locality of the relativistic effect. Numerical assessments of the LUT scheme were performed in diatomic molecules such as HX and X(2) (X = F, Cl, Br, I, and At) and hydrogen halide clusters, (HX)(n) (X = F, Cl, Br, and I). Total energies obtained by the LUT method agree well with conventional IODKH results. The computational costs of the LUT method are drastically lower than those of conventional methods since in the former there is linear-scaling with respect to the system size and a small prefactor.

Extension of local response dispersion method to excited-state calculation based on time-dependent density functional theory.

Ikabata Yasuhiro;Nakai Hiromi

The Journal of chemical physics 137(12) 2012-2012

PubMed

Detail

ISSN:1089-7690

Outline::We report the extension of the local response dispersion (LRD) method to the excited-state calculation based on time-dependent density functional theory. The difference density matrix, which is usually used for excited-state response properties, enables a state-specific dispersion correction. The numerical assessment proves that interaction energies of exciton-localized molecular complexes and their shifts from the ground state are accurately reproduced by the LRD method. Furthermore, we find that the dispersion correction is important in reproducing binding energies of aromatic excimers, despite the existence of other attractive forces such as exciton delocalization and charge-transfer interaction.

Cristaxenicin A, an antiprotozoal xenicane diterpenoid from the deep sea gorgonian Acanthoprimnoa cristata.

Ishigami Shin-Taro;Goto Yasuyuki;Inoue Noboru;Kawazu Shin-Ichiro;Matsumoto Yoshitsugu;Imahara Yukimitsu;Tarumi Moto;Nakai Hiromi;Fusetani Nobuhiro;Nakao Yoichi

Cristaxenicin A, an antiprotozoal xenicane diterpenoid from the deep sea gorgonian Acanthoprimnoa cristata. 77(23) 2012-2012

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ISSN:1520-6904

Outline::A new xenicane diterpenoid, cristaxenicin A (1), has been isolated from the deep sea gorgonian Acanthoprimnoa cristata. The structure of 1 was elucidated on the basis of spectral analysis including NMR and MS. The absolute configuration of 1 was determined on the basis of quantum chemical calculation of CD spectra. Cristaxenicin A (1) showed antiprotozoal activities against Leishmania amazonensis and Trypanosoma congolense with IC(50) values of 0.088 and 0.25 μM, respectively.

Local unitary transformation method for large-scale two-component relativistic calculations. II. Extension to two-electron Coulomb interaction.

Seino Junji;Nakai Hiromi

Local unitary transformation method for large-scale two-component relativistic calculations. II. Extension to two-electron Coulomb interaction. 137(14) 2012-2012

DOI

Detail

ISSN:1089-7690

Outline::The local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012)], which is based on the locality of relativistic effects, has been extended to a four-component Dirac-Coulomb Hamiltonian. In the previous study, the LUT scheme was applied only to a one-particle IODKH Hamiltonian with non-relativistic two-electron Coulomb interaction, termed IODKH/C. The current study extends the LUT scheme to a two-particle IODKH Hamiltonian as well as one-particle one, termed IODKH/IODKH, which has been a real bottleneck in numerical calculation. The LUT scheme with the IODKH/IODKH Hamiltonian was numerically assessed in the diatomic molecules HX and X(2) and hydrogen halide molecules, (HX)(n) (X = F, Cl, Br, and I). The total Hartree-Fock energies calculated by the LUT method agree well with conventional IODKH/IODKH results. The computational cost of the LUT method is reduced drastically compared with that of the conventional method. In addition, the LUT method achieves linear-scaling with respect to the system size and a small prefactor.

An effective energy gradient expression for divide-and-conquer second-order Møller-Plesset perturbation theory.

Kobayashi Masato;Nakai Hiromi

An effective energy gradient expression for divide-and-conquer second-order Møller-Plesset perturbation theory. 138(4) 2013-2013

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ISSN:1089-7690

Outline::We recently proposed a linear-scaling evaluation scheme for the second-order Mo̸ller-Plesset perturbation (MP2) energy based on the divide-and-conquer (DC) method [M. Kobayashi, Y. Imamura, and H. Nakai, J. Chem. Phys. 127, 074103 (2007)]. In this paper, we propose an approximate but effective expression for the first derivative of the DC-MP2 energy. The present scheme evaluates the one- and two-body density matrices, which appear in the MP2 gradient formula, in the DC manner; that is, the entire matrix is obtained as the sum of subsystem matrices masked by the partition matrix. Therefore, the method requires solving only the local Z-vector equations. Illustrative applications to three types of systems, peptides, Si surface model, and delocalized polyenes, reveal the effectiveness of the present method.

Linearity condition for orbital energies in density functional theory (III): benchmark of total energies.

Imamura Yutaka;Kobayashi Rie;Nakai Hiromi

Linearity condition for orbital energies in density functional theory (III): benchmark of total energies. 34(14) 2013-2013

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ISSN:1096-987X

Outline::This study presents a numerical assessment of total energy related physical quantities estimated using the orbital-specific (OS) global and range-separated hybrid functionals, designed to satisfy the linearity condition for orbital energies (LCOE). The numerical assessment demonstrates that accurate evaluation of the reaction energies, reaction barrier, and dissociation curve can be achieved via the OS hybrid functional, for systems in which self-interaction is expected to be dominant. Therefore, the LCOE offers an accurate description of orbital energies as well as total energies for self-interaction dominant systems.

Novel approach to excited-state calculations of large molecules based on divide-and-conquer method: application to photoactive yellow protein.

Yoshikawa Takeshi;Kobayashi Masato;Fujii Atsuhiko;Nakai Hiromi

Novel approach to excited-state calculations of large molecules based on divide-and-conquer method: application to photoactive yellow protein. 117(18) 2013-2013

DOI

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ISSN:1520-5207

Outline::In this study, the divide-and-conquer (DC) method is extended to configuration-interaction singles, time-dependent density functional, and symmetry-adapted cluster configuration interaction (SACCI) theories for enabling excited-state calculations of large systems. In DC-based excited-state theories, one subsystem is selected as the excitation subsystem and analyzed via excited-state calculations. Test calculations for formaldehyde in water and a conjugated aldehyde demonstrate the high accuracy and effectiveness of these methods. To demonstrate the efficiency of the method, we calculated the π-π* excited state of photoactive yellow protein (PYP). The numerical applications to PYP confirm that the DC-SACCI method significantly accelerates the excited-state calculations while maintaining high accuracy.

Local unitary transformation method toward practical electron correlation calculations with scalar relativistic effect in large-scale molecules.

Seino Junji;Nakai Hiromi

Local unitary transformation method toward practical electron correlation calculations with scalar relativistic effect in large-scale molecules. 139(3) 2013-2013

DOI

Detail

ISSN:1089-7690

Outline::In order to perform practical electron correlation calculations, the local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012); and ibid. 137, 144101 (2012)], which is based on the locality of relativistic effects, has been combined with the linear-scaling divide-and-conquer (DC)-based Hartree-Fock (HF) and electron correlation methods, such as the second-order Mo̸ller-Plesset (MP2) and the coupled cluster theories with single and double excitations (CCSD). Numerical applications in hydrogen halide molecules, (HX)n (X = F, Cl, Br, and I), coinage metal chain systems, Mn (M = Cu and Ag), and platinum-terminated polyynediyl chain, trans,trans-{(p-CH3C6H4)3P}2(C6H5)Pt(C≡C)4Pt(C6H5){(p-CH3C6H4)3P}2, clarified that the present methods, namely DC-HF, MP2, and CCSD with the LUT-IODKH Hamiltonian, reproduce the results obtained using conventional methods with small computational costs. The combination of both LUT and DC techniques could be the first approach that achieves overall quasi-linear-scaling with a small prefactor for relativistic electron correlation calculations.

Kinetic energy decomposition scheme based on information theory.

Imamura Yutaka;Suzuki Jun;Nakai Hiromi

Kinetic energy decomposition scheme based on information theory. 34(32) 2013-2013

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ISSN:1096-987X

Outline::We proposed a novel kinetic energy decomposition analysis based on information theory. Since the Hirshfeld partitioning for electron densities can be formulated in terms of Kullback-Leibler information deficiency in information theory, a similar partitioning for kinetic energy densities was newly proposed. The numerical assessments confirm that the current kinetic energy decomposition scheme provides reasonable chemical pictures for ionic and covalent molecules, and can also estimate atomic energies using a correction with viral ratios.

Analytical energy gradient based on spin-free infinite-order Douglas-Kroll-Hess method with local unitary transformation.

Nakajima Yuya;Seino Junji;Nakai Hiromi

Analytical energy gradient based on spin-free infinite-order Douglas-Kroll-Hess method with local unitary transformation. 139(24) 2013-2013

DOI

Detail

ISSN:1089-7690

Outline::In this study, the analytical energy gradient for the spin-free infinite-order Douglas-Kroll-Hess (IODKH) method at the levels of the Hartree-Fock (HF), density functional theory (DFT), and second-order Møller-Plesset perturbation theory (MP2) is developed. Furthermore, adopting the local unitary transformation (LUT) scheme for the IODKH method improves the efficiency in computation of the analytical energy gradient. Numerical assessments of the present gradient method are performed at the HF, DFT, and MP2 levels for the IODKH with and without the LUT scheme. The accuracies are examined for diatomic molecules such as hydrogen halides, halogen dimers, coinage metal (Cu, Ag, and Au) halides, and coinage metal dimers, and 20 metal complexes, including the fourth-sixth row transition metals. In addition, the efficiencies are investigated for one-, two-, and three-dimensional silver clusters. The numerical results confirm the accuracy and efficiency of the present method.

Acceleration of self-consistent field convergence in ab initio molecular dynamics simulation with multiconfigurational wave function.

Okoshi Masaki;Nakai Hiromi

Acceleration of self-consistent field convergence in ab initio molecular dynamics simulation with multiconfigurational wave function. 35(20) 2014-2014

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Detail

ISSN:1096-987X

Outline::The Lagrange interpolation of molecular orbital (LIMO) method, which reduces the number of self-consistent field iterations in ab initio molecular dynamics simulations with the Hartree-Fock method and the Kohn-Sham density functional theories, is extended to the theory of multiconfigurational wave functions. We examine two types of treatments for the active orbitals that are partially occupied. The first treatment, as denoted by LIMO(C), is a simple application of the conventional LIMO method to the union of the inactive core and the active orbitals. The second, as denoted by LIMO(S), separately treats the inactive core and the active orbitals. Numerical tests to compare the two treatments clarify that LIMO(S) is superior to LIMO(C). Further applications of LIMO(S) to various systems demonstrate its effectiveness and robustness.

Extension of accompanying coordinate expansion and recurrence relation method for general-contraction basis sets.

Hayami Masao;Seino Junji;Nakai Hiromi

Extension of accompanying coordinate expansion and recurrence relation method for general-contraction basis sets. 35(20) 2014-2014

DOI

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ISSN:1096-987X

Outline::An algorithm of the accompanying coordinate expansion and recurrence relation (ACE-RR), which is used for the rapid evaluation of the electron repulsion integral (ERI), has been extended to the general-contraction (GC) scheme. The present algorithm, denoted by GC-ACE-RR, is designed for molecular calculations including heavy elements, whose orbitals consist of many primitive functions with and without higher angular momentum such as d- and f-orbitals. The performance of GC-ACE-RR was assessed for (ss|ss)-, (pp|pp)-, (dd|dd)-, and (ff|ff)-type ERIs in terms of contraction length and the number of GC orbitals. The present algorithm was found to reduce the central processing unit time compared with the ACE-RR algorithm, especially for higher angular momentum and highly contracted orbitals. Compared with HONDOPLUS and GAMESS program packages, GC-ACE-RR computations for ERIs of three-dimensional gold clusters Aun (n = 1, 2, …, 10, 15, 20, and 25) are more than 10 times faster.

Quantum chemical approach for condensed-phase thermochemistry: proposal of a harmonic solvation model.

Nakai Hiromi;Ishikawa Atsushi

Quantum chemical approach for condensed-phase thermochemistry: proposal of a harmonic solvation model. 141(17) 2014-2014

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ISSN:1089-7690

Outline::We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor-liquid equilibration of water and ethanol, and dissolution of gaseous CO2 in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

Linear-scaling self-consistent field calculations based on divide-and-conquer method using resolution-of-identity approximation on graphical processing units.

Yoshikawa Takeshi;Nakai Hiromi

Journal of computational chemistry 36(3) 2015-2015

PubMedDOI

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ISSN:1096-987X

Outline::Graphical processing units (GPUs) are emerging in computational chemistry to include Hartree-Fock (HF) methods and electron-correlation theories. However, ab initio calculations of large molecules face technical difficulties such as slow memory access between central processing unit and GPU and other shortfalls of GPU memory. The divide-and-conquer (DC) method, which is a linear-scaling scheme that divides a total system into several fragments, could avoid these bottlenecks by separately solving local equations in individual fragments. In addition, the resolution-of-the-identity (RI) approximation enables an effective reduction in computational cost with respect to the GPU memory. The present study implemented the DC-RI-HF code on GPUs using math libraries, which guarantee compatibility with future development of the GPU architecture. Numerical applications confirmed that the present code using GPUs significantly accelerated the HF calculations while maintaining accuracy.

Local response dispersion method in periodic systems: Implementation and assessment.

Ikabata Yasuhiro;Tsukamoto Yusuke;Imamura Yutaka;Nakai Hiromi

Journal of computational chemistry 36(5) 2015-2015

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ISSN:1096-987X

Outline::We report the implementation of the local response dispersion (LRD) method in an electronic structure program package aimed at periodic systems and an assessment combined with the Perdew-Burke-Ernzerhof (PBE) functional and its revised version (revPBE). The real-space numerical integration was implemented and performed exploiting the electron distribution given by the plane-wave basis set. The dispersion-corrected density functionals revPBE+LRD was found to be suitable for reproducing energetics, structures, and electron distributions in simple substances, molecular crystals, and physical adsorptions.

Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals.

Cho Daeheum;Ko Kyoung Chul;Ikabata Yasuhiro;Wakayama Kazufumi;Yoshikawa Takeshi;Nakai Hiromi;Lee Jin Yong

The Journal of chemical physics 142(2) 2015-2015

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ISSN:1089-7690

Outline::The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH&HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

Revisiting the extrapolation of correlation energies to complete basis set limit.

Okoshi Masaki;Atsumi Teruo;Nakai Hiromi

Journal of computational chemistry 36(14) 2015-2015

PubMedDOI

Detail

ISSN:1096-987X

Outline::The extrapolation scheme of correlation energy is revisited to evaluate the complete basis set limit from double-zeta (DZ) and triple-zeta levels of calculations. The DZ level results are adjusted to the standard asymptotic behavior with respect to the cardinal number, observed at the higher levels of basis sets. Two types of adjusting schemes with effective scaling factors, which recover errors in extrapolations with the DZ level basis set, are examined. The first scheme scales the cardinal number for the DZ level energy, while the second scheme scales the prefactor of the extrapolation function. Systematic assessments on the Gaussian-3X and Gaussian-2 test sets reveal that these calibration schemes successfully and drastically reduce errors without additional computational efforts.

Accompanying coordinate expansion and recurrence relation method using a transfer relation scheme for electron repulsion integrals with high angular momenta and long contractions.

Hayami Masao;Seino Junji;Nakai Hiromi

The Journal of chemical physics 142(20) 2015-2015

PubMedDOI

Detail

ISSN:1089-7690

Outline::An efficient algorithm for the rapid evaluation of electron repulsion integrals is proposed. The present method, denoted by accompanying coordinate expansion and transferred recurrence relation (ACE-TRR), is constructed using a transfer relation scheme based on the accompanying coordinate expansion and recurrence relation method. Furthermore, the ACE-TRR algorithm is extended for the general-contraction basis sets. Numerical assessments clarify the efficiency of the ACE-TRR method for the systems including heavy elements, whose orbitals have long contractions and high angular momenta, such as f- and g-orbitals.

A divide-and-conquer method with approximate Fermi levels for parallel computations

Yoshikawa, Takeshi; Yoshikawa, Takeshi; Yoshikawa, Takeshi; Yoshikawa, Takeshi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Theoretical Chemistry Accounts 134(5) 2015/05-2015/05

DOIScopus

Detail

ISSN:1432881X

Outline:© 2015, Springer-Verlag Berlin Heidelberg. This study proposes two efficient algorithms of the linear-scaling divide-and-conquer self-consistent field (DC-SCF) method for parallel computations. These algorithms minimize the amount of network communication required for determining the common Fermi level by adopting an approximate Fermi level. One algorithm adopts the quasi-converged Fermi level during DC-SCF iterations, while the other uses the quasi-converged electron numbers of individual subsystems. A numerical assessment demonstrates the high parallel efficiency for both methods without loss in accuracy.

Revisiting the extrapolation of correlation energies to complete basis set limit

Okoshi, Masaki; Atsumi, Teruo; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Computational Chemistry 36(14) p.1075 - 10822015/05-2015/05

DOIScopus

Detail

ISSN:01928651

Outline:© 2015 Wiley Periodicals, Inc. The extrapolation scheme of correlation energy is revisited to evaluate the complete basis set limit from double-zeta (DZ) and triple-zeta levels of calculations. The DZ level results are adjusted to the standard asymptotic behavior with respect to the cardinal number, observed at the higher levels of basis sets. Two types of adjusting schemes with effective scaling factors, which recover errors in extrapolations with the DZ level basis set, are examined. The first scheme scales the cardinal number for the DZ level energy, while the second scheme scales the prefactor of the extrapolation function. Systematic assessments on the Gaussian-3X and Gaussian-2 test sets reveal that these calibration schemes successfully and drastically reduce errors without additional computational efforts.

Accompanying coordinate expansion and recurrence relation method using a transfer relation scheme for electron repulsion integrals with high angular momenta and long contractions

Hayami, Masao; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Chemical Physics 142(20) 2015/05-2015/05

DOIScopus

Detail

ISSN:00219606

Outline:© 2015 AIP Publishing LLC. An efficient algorithm for the rapid evaluation of electron repulsion integrals is proposed. The present method, denoted by accompanying coordinate expansion and transferred recurrence relation (ACE-TRR), is constructed using a transfer relation scheme based on the accompanying coordinate expansion and recurrence relation method. Furthermore, the ACE-TRR algorithm is extended for the general-contraction basis sets. Numerical assessments clarify the efficiency of the ACE-TRR method for the systems including heavy elements, whose orbitals have long contractions and high angular momenta, such as f- and g-orbitals.

Divide-and-Conquer-Type Density-Functional Tight-Binding Molecular Dynamics Simulations of Proton Diffusion in a Bulk Water System

Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Sakti, Aditya Wibawa; Nishimura, Yoshifumi; Nishimura, Yoshifumi

Journal of Physical Chemistry B 120(1) p.217 - 2212016/01-2016/01

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Detail

ISSN:15206106

Outline:© 2015 American Chemical Society.The process of proton diffusion in liquid water was investigated using molecular dynamics (MD) simulations, and the total energy and atomic forces were evaluated by the divide-and-conquer-type density-functional tight-binding (DC-DFTB) method. The effectiveness of this approach was confirmed by comparing the computational time of water clusters with conventional treatments. The unit cell employed herein, which contained 523 water molecules and 1 excess proton, was moderately large in comparison with those used in previous studies. The reasonable accuracy obtained by using this unit cell was confirmed by examining the temperature fluctuation. The diffusion coefficients for the vehicular and Grotthuss processes were accurately reproduced by the DC-DFTB-MD simulations with the unit cell containing 523 water molecules. Furthermore, the energy barriers were evaluated from the temperature dependence of the diffusion coefficient for each process. The calculated barrier for Grotthuss diffusion was in good agreement with the experimental value.

Contrasting mechanisms for CO2 absorption and regeneration processes in aqueous amine solutions: Insights from density-functional tight-binding molecular dynamics simulations

Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nishimura, Yoshifumi; Nishimura, Yoshifumi; Kaiho, Takeaki; Kubota, Takahito; Sato, Hiroshi

Chemical Physics Letters 647p.127 - 1312016/03-2016/03

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ISSN:00092614

Outline:© 2016 Elsevier B.V. All rights reserved.CO2 chemical absorption and regeneration processes in aqueous amine solutions were investigated using density-functional tight-binding molecular dynamics simulations. Extensive analyses of the structural, electronic, and dynamical properties of 100 independent trajectories supported the contrasting mechanisms in the absorption and regeneration processes. In the CO2 absorption process, bicarbonate formed where the hydroxyl anion migrated through the hydrogen-bond network of water molecules, namely, by a Grotthuss-type mechanism. On the other hand, direct proton transfer from the protonated amine to the hydroxyl group of bicarbonate, which is called the ion-pair mechanism, was the key step to the release of CO2.

Quantum chemical approach for condensed-phase thermochemistry (III): Accurate evaluation of proton hydration energy and standard hydrogen electrode potential

Ishikawa, Atsushi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 650p.159 - 1642016/04-2016/04

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ISSN:00092614

Outline:© 2016 Elsevier B.V. All rights reserved. Gibbs free energy of hydration of a proton and standard hydrogen electrode potential were evaluated using high-level quantum chemical calculations. The solvent effect was included using the cluster-continuum model, which treated short-range effects by quantum chemical calculations of proton-water complexes, and the long-range effects by a conductor-like polarizable continuum model. The harmonic solvation model (HSM) was employed to estimate enthalpy and entropy contributions due to nuclear motions of the clusters by including the cavity-cluster interactions. Compared to the commonly used ideal gas model, HSM treatment significantly improved the contribution of entropy, showing a systematic convergence toward the experimental data.

Electronic transition process of fluorescence appearing in various organic polymers

Nishikawa, Seiya; Tonoi, Masashi; Yoshikawa, Takeshi; Hirai, Naoshi; Nakai, Hiromi; Ohki, Yoshimichi; Ohki, Yoshimichi

IEEJ Transactions on Fundamentals and Materials 136(4) p.205 - 2112016/01-2016/01

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ISSN:03854205

Outline:© 2016 The Institute of Electrical Engineers of Japan.Low density polyethylene (LDPE) and polypropylene (PP) exhibit a photoluminescence (PL) band, which emits photons with an energy of around 4.3 eV when excited by photons with energies around 6.4 eV. The origin of this PL band has been assigned to α, β -unsaturated carbonyl. In this paper, the appearance of PL was examined for four kinds of polyolefin and four kinds of biodegradable polymers. As a result, it has become clear that all the polymers show a PL band with a PL excitation spectrum and a PL spectrum similar to those of the above-mentioned PL band in LDPE and PP. The decay profiles observed for these PL bands indicate that they are fluorescence. Furthermore, the intensity of the PL becomes weak for all the four polyolefin samples and the polylatic acid sample if ultraviolet photons were irradiated to the sample. Quantum chemical calculations carried out by assuming a model of α, β -unsaturated carbonyl have revealed that the PL originates in the π∗to π transition of electrons in the carbon-carbon double bond.

Implementation of Analytical Energy Gradient of Spin-Dependent General Hartree-Fock Method Based on the Infinite-Order Douglas-Kroll-Hess Relativistic Hamiltonian with Local Unitary Transformation

Nakajima, Yuya; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Chemical Theory and Computation 12(5) p.2181 - 21902016/05-2016/05

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ISSN:15499618

Outline:© 2016 American Chemical Society.An analytical energy gradient for the spin-dependent general Hartree-Fock method based on the infinite-order Douglas-Kroll-Hess (IODKH) method was developed. To treat realistic systems, the local unitary transformation (LUT) scheme was employed both in energy and energy gradient calculations. The present energy gradient method was numerically assessed to investigate the accuracy in several diatomic molecules containing fifth- and sixth-period elements and to examine the efficiency in one-, two-, and three-dimensional silver clusters. To arrive at a practical calculation, we also determined the geometrical parameters of fac-tris(2-phenylpyridine)iridium and investigated the efficiency. The numerical results confirmed that the present method describes a highly accurate relativistic effect with high efficiency. The present method can be a powerful scheme for determining geometries of large molecules, including heavy-element atoms.

Quantum chemical approach for condensed-phase thermochemistry (IV): Solubility of gaseous molecules

Ishikawa, Atsushi; Kamata, Masahiro; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 655-656p.103 - 1092016/07-2016/07

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ISSN:00092614

Outline:© 2016 Elsevier B.V. All rights reserved.The harmonic solvation model (HSM) was applied to the solvation of gaseous molecules and compared to a procedure based on the ideal gas model (IGM). Examination of 25 molecules showed that (i) the accuracy of ΔGsolv was similar for both methods, but the HSM shows advantages for calculating ΔHsolv and TΔSsolv; (ii) TΔSsolv contributes more than ΔHsolv to ΔGsolv in the HSM, i.e. the solvation of gaseous molecules is entropy-driven, which agrees well with experimental understanding (the IGM does not show this); (iii) the temperature dependence of Henry's law coefficient was correctly reproduced with the HSM.

Assessment of self-consistent field convergence in spin-dependent relativistic calculations

Nakano, Masahiko; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 657p.65 - 712016/07-2016/07

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ISSN:00092614

Outline:© 2016 Elsevier B.V. All rights reserved.This Letter assesses the self-consistent field (SCF) convergence behavior in the generalized Hartree-Fock (GHF) method. Four acceleration algorithms were implemented for efficient SCF convergence in the GHF method: the damping algorithm, the conventional direct inversion in the iterative subspace (DIIS), the energy-DIIS (EDIIS), and a combination of DIIS and EDIIS. Four different systems with varying complexity were used to investigate the SCF convergence using these algorithms, ranging from atomic systems to metal complexes. The numerical assessments demonstrated the effectiveness of a combination of DIIS and EDIIS for GHF calculations in comparison with the other discussed algorithms.

Three pillars for achieving quantum mechanical molecular dynamics simulations of huge systems: Divide-and-conquer, density-functional tight-binding, and massively parallel computation

Nishizawa, Hiroaki; Nishimura, Yoshifumi; Nishimura, Yoshifumi; Kobayashi, Masato; Kobayashi, Masato; Kobayashi, Masato; Irle, Stephan; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Computational Chemistry p.1983 - 19922016/08-2016/08

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ISSN:01928651

Outline:© 2016 Wiley Periodicals, Inc.The linear-scaling divide-and-conquer (DC) quantum chemical methodology is applied to the density-functional tight-binding (DFTB) theory to develop a massively parallel program that achieves on-the-fly molecular reaction dynamics simulations of huge systems from scratch. The functions to perform large scale geometry optimization and molecular dynamics with DC-DFTB potential energy surface are implemented to the program called DC-DFTB-K. A novel interpolation-based algorithm is developed for parallelizing the determination of the Fermi level in the DC method. The performance of the DC-DFTB-K program is assessed using a laboratory computer and the K computer. Numerical tests show the high efficiency of the DC-DFTB-K program, a single-point energy gradient calculation of a one-million-atom system is completed within 60 s using 7290 nodes of the K computer. © 2016 Wiley Periodicals, Inc.

Quantum chemical approach for condensed-phase thermochemistry (III): Accurate evaluation of proton hydration energy and standard hydrogen electrode potential

Ishikawa, Atsushi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 2015/12-2015/12

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ISSN:00092614

Outline:© 2016 Elsevier B.V.Gibbs free energy of hydration of a proton and standard hydrogen electrode potential were evaluated using high-level quantum chemical calculations. The solvent effect was included using the cluster-continuum model, which treated short-range effects by quantum chemical calculations of proton-water complexes, and the long-range effects by a conductor-like polarizable continuum model. The harmonic solvation model (HSM) was employed to estimate enthalpy and entropy contributions due to nuclear motions of the clusters by including the cavity-cluster interactions. Compared to the commonly used ideal gas model, HSM treatment significantly improved the contribution of entropy, showing a systematic convergence toward the experimental data.

Quantum chemistry beyond Born–Oppenheimer approximation on a quantum computer: A simulated phase estimation study

Veis, Libor; Višňák, Jakub; Nishizawa, Hiroaki; Nakai, Hiromi; Pittner, Jiří

International Journal of Quantum Chemistry 116(18) p.1328 - 13362016/09-2016/09

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ISSN:00207608

Outline:© 2016 Wiley Periodicals, Inc.We present an efficient quantum algorithm for beyond-Born–Oppenheimer molecular energy computations. Our approach combines the quantum full configuration interaction method with the nuclear orbital plus molecular orbital method. We give the details of the algorithm and demonstrate its performance by classical simulations. Two isotopomers of the hydrogen molecule (H2, HT) were chosen as representative examples and calculations of the lowest rotationless vibrational transition energies were simulated. © 2016 Wiley Periodicals, Inc.

Informatics-Based Energy Fitting Scheme for Correlation Energy at Complete Basis Set Limit

Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Computational Chemistry p.2304 - 23152016/09-2016/09

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ISSN:01928651

Outline:© 2016 Wiley Periodicals, Inc.Energy fitting schemes based on informatics techniques using hierarchical basis sets with small cardinal numbers were numerically investigated to estimate correlation energies at the complete basis set limits. Numerical validations confirmed that the conventional two-point extrapolation models can be unified into a simple formula with optimal parameters obtained by the same test sets. The extrapolation model was extended to two-point fitting models by a relaxation of the relationship between the extrapolation coefficients or a change of the fitting formula. Furthermore, n-scheme fitting models were developed by the combinations of results calculated at several theory levels and basis sets to compensate for the deficiencies in the fitting model at one level of theory. Systematic assessments on the Gaussian-3X and Gaussian-2 sets revealed that the fitting models drastically reduced errors with equal or smaller computational effort. © 2016 Wiley Periodicals, Inc.

Efficient two-component relativistic method for large systems

Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

AIP Conference Proceedings 17022015/12-2015/12

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ISSN:0094243X

Outline:© 2015 AIP Publishing LLC.This paper reviews a series of theoretical studies to develop efficient two-component (2c) relativistic method for large systems by the author's group. The basic theory is the infinite-order Douglas-Kroll-Hess (IODKH) method for many-electron Dirac-Coulomb Hamiltonian. The local unitary transformation (LUT) scheme can effectively produce the 2c relativistic Hamiltonian, and the divide-and-conquer (DC) method can achieve linear-scaling of Hartree-Fock and electron correlation methods. The frozen core potential (FCP) theoretically connects model potential calculations with the all-electron ones. The accompanying coordinate expansion with a transfer recurrence relation (ACE-TRR) scheme accelerates the computations of electron repulsion integrals with high angular momenta and long contractions.

Relativistic frozen core potential scheme with relaxation of core electrons

Nakajima, Yuya; Seino, Junji; Hayami, Masao; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 663p.97 - 1032016/10-2016/10

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ISSN:00092614

Outline:© 2016 Elsevier B.V.This letter proposes a relaxation scheme for core electrons based on the frozen core potential method at the infinite-order Douglas–Kroll–Hess level, called FCP-CR. The core electrons are self-consistently relaxed using frozen molecular valence potentials after the valence SCF calculation is performed. The efficiency of FCP-CR is confirmed by calculations of gold clusters. Furthermore, FCP-CR reproduces the results of the all-electron method for the energies of coinage metal dimers and the core ionization energies and core level shifts of vinyl acetate and three tungsten complexes at the Hartree–Fock and/or symmetry-adapted cluster configuration interaction levels.

The divide-and-conquer second-order proton propagator method based on nuclear orbital plus molecular orbital theory for the efficient computation of proton binding energies

Tsukamoto, Yusuke; Ikabata, Yasuhiro; Romero, Jonathan; Romero, Jonathan; Reyes, Andrés; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Physical Chemistry Chemical Physics 18(39) p.27422 - 274312016/01-2016/01

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ISSN:14639076

Outline:© 2016 the Owner Societies. An efficient computational method to evaluate the binding energies of many protons in large systems was developed. Proton binding energy is calculated as a corrected nuclear orbital energy using the second-order proton propagator method, which is based on nuclear orbital plus molecular orbital theory. In the present scheme, the divide-and-conquer technique was applied to utilize local molecular orbitals. This use relies on the locality of electronic relaxation after deprotonation and the electron-nucleus correlation. Numerical assessment showed reduction in computational cost without the loss of accuracy. An initial application to model a protein resulted in reasonable binding energies that were in accordance with the electrostatic environment and solvent effects.

Efficient pole-search algorithm for dynamic polarizability: Toward alternative excited-state calculation for large systems

Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Yoshikawa, Takeshi; Nonaka, Yutaro

Journal of Computational Chemistry 38(1) p.7 - 142017/01-2017/01

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ISSN:01928651

Outline:© 2016 Wiley Periodicals, Inc.This study presents an efficient algorithm to search for the poles of dynamic polarizability to obtain excited states of large systems with nonlocal excitation nature. The present algorithm adopts a homogeneous search with a constant frequency interval and a bisection search to achieve high accuracy. Furthermore, the subtraction process of the information about the detected poles from the total dynamic polarizability is used to extract the undetected pole contributions. Numerical assessments confirmed the accuracy and efficiency of the present algorithm in obtaining the excitation energies and oscillator strengths of all dipole-allowed excited states. A combination of the present pole-search algorithm and divide-and-conquer-based dynamic polarizability calculations was found to be promising to treat nonlocal excitations of large systems. © 2016 Wiley Periodicals, Inc.

Relativistic effect on enthalpy of formation for transition-metal complexes

Nakajima, Yuya; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 673p.24 - 292017/04-2017/04

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ISSN:00092614

Outline:© 2017 Elsevier B.V.This Letter examines the enthalpy of formation for 12 transition metal diatomic molecules and 23 transition metal complexes from the viewpoint of effect of the relativistic effect by using the infinite-order Douglas–Kroll–Hess method with the local unitary transformation and three types of pseudopotentials for several levels of theory. The spin-orbit effect contribution to the enthalpy of formation is more than 10 kcal/mol for third transition metal complexes. Frozen orbital approximation at the outermost orbitals in pseudopotential methods shows a contribution to the enthalpy of formation that is more than two times larger than those of inner core orbitals.

Development of spin-dependent relativistic open-shell Hartree–Fock theory with time-reversal symmetry (I): The unrestricted approach

Nakano, Masahiko; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

International Journal of Quantum Chemistry 117(10) 2017/05-2017/05

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ISSN:00207608

Outline:© 2017 Wiley Periodicals, Inc. An open-shell Hartree–Fock (HF) theory for spin-dependent, two-component relativistic calculations, termed the Kramers-unrestricted HF (KUHF) method, is developed. The present KUHF method, which is formulated as a relativistic counterpart of nonrelativistic UHF, is based on quaternion algebra and partly uses time-reversal symmetry. The fundamental characteristics of KUHF are discussed in this study. From numerical assessments, it was revealed that KUHF gives a corresponding solution to nonrelativistic UHF; furthermore, KUHF properly describes spin-orbit interactions. In addition, KUHF can improve the self-consistent field convergence behavior in spin-dependent calculations, for example, for f-block elements.

Unveiling a New Aspect of Simple Arylboronic Esters: Long-Lived Room-Temperature Phosphorescence from Heavy-Atom-Free Molecules

Shoji, Yoshiaki; Ikabata, Yasuhiro; Wang, Qi; Wang, Qi; Nemoto, Daisuke; Sakamoto, Atsushi; Tanaka, Naoki; Seino, Junji; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Fukushima, Takanori

Journal of the American Chemical Society 139(7) p.2728 - 27332017/02-2017/02

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ISSN:00027863

Outline:© 2017 American Chemical Society. Arylboronic esters can be used as versatile reagents in organic synthesis, as represented by Suzuki-Miyaura cross-coupling. Here we report a serendipitous finding that simple arylboronic esters are phosphorescent in the solid state at room temperature with a lifetime on the order of several seconds. The phosphorescence properties of arylboronic esters are remarkable in light of the general notion that phosphorescent organic molecules require heavy atoms and/or carbonyl groups for the efficient generation of a triplet excited state. Theoretical calculations on phenylboronic acid pinacol ester indicated that this molecule undergoes an out-of-plane distortion at the (pinacol)B-Cipsomoiety in the T1excited state, which is responsible for its phosphorescence. A compound survey with 19 arylboron compounds suggested that the phosphorescence properties might be determined by solid-state molecular packing rather than by the patterns and numbers of boron substituents on the aryl units. The present finding may update the general notion of phosphorescent organic molecules.

Development of spin-dependent relativistic open-shell Hartree–Fock theory with time-reversal symmetry (II): The restricted open-shell approach

Nakano, Masahiko; Nakamura, Ryota; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

International Journal of Quantum Chemistry 117(10) 2017/05-2017/05

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ISSN:00207608

Outline:© 2017 Wiley Periodicals, Inc. An open-shell Hartree–Fock (HF) theory for spin-dependent two-component relativistic calculations, termed the Kramers-restricted open-shell HF (KROHF) method, is developed. The present KROHF method is defined as a relativistic analogue of ROHF using time-reversal symmetry and quaternion algebra, based on the Kramers-unrestricted HF (KUHF) theory reported in our previous study (Int. J. Quantum Chem., doi:10.1002/qua.25356). As seen in the nonrelativistic ROHF theory, the ambiguity of the KROHF Fock operator gives physically meaningless spinor energies. To avoid this problem, the canonical parametrization of KROHF to satisfy Koopmans' theorem is also discussed based on the procedure proposed by Plakhutin et al. (J. Chem. Phys. 2006, 125, 204110). Numerical assessments confirmed that KROHF using Plakhutin's canonicalization procedure correctly gives physical spinor energies within the frozen-orbital approximation under spin–orbit interactions.

Universal formulation of second-order generalized MØller–Plesset perturbation theory for a spin-dependent two-component relativistic many-electron Hamiltonian

Nakano, Masahiko; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 675p.137 - 1442017/01-2017/01

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ISSN:00092614

Outline:© 2017 Elsevier B.V.We have derived and implemented a universal formulation of the second-order generalized Møller–Plesset perturbation theory (GMP2) for spin-dependent (SD) two-component relativistic many-electron Hamiltonians, such as the infinite-order Douglas–Kroll–Hess Hamiltonian for many-electron systems, which is denoted as IODKH/IODKH. Numerical assessments for He- and Ne-like atoms and 16 diatomic molecules show that the MP2 correlation energies with IODKH/IODKH agree well with those calculated with the four-component Dirac–Coulomb (DC) Hamiltonian, indicating a systematic improvement on the inclusion of relativistic two-electron terms. The present MP2 scheme for IODKH/IODKH is demonstrated to be computationally more efficient than that for DC.

Development of an excited-state calculation method for large systems using dynamical polarizability: A divide-and-conquer approach at the time-dependent density functional level

Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Yoshikawa, Takeshi

Journal of Chemical Physics 146(12) 2017/03-2017/03

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ISSN:00219606

Outline:© 2017 Author(s). In this study, we developed an excited-state calculation method for large systems using dynamical polarizabilities at the time-dependent density functional theory level. Three equivalent theories, namely, coupled-perturbed self-consistent field (CPSCF), random phase approximation (RPA), and Green function (GF), were extended to linear-scaling methods using the divide-and-conquer (DC) technique. The implementations of the standard and DC-based CPSCF, RPA, and GF methods are described. Numerical applications of these methods to polyene chains, single-wall carbon nanotubes, and water clusters confirmed the accuracy and efficiency of the DC-based methods, especially DC-GF.

Relativistic density functional theory with picture-change corrected electron density based on infinite-order Douglas-Kroll-Hess method

Oyama, Takuro; Ikabata, Yasuhiro; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Chemical Physics Letters 680p.37 - 432017/01-2017/01

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ISSN:00092614

Outline:© 2017 Elsevier B.V. This Letter proposes a density functional treatment based on the two-component relativistic scheme at the infinite-order Douglas-Kroll-Hess (IODKH) level. The exchange-correlation energy and potential are calculated using the electron density based on the picture-change corrected density operator transformed by the IODKH method. Numerical assessments indicated that the picture-change uncorrected density functional terms generate significant errors, on the order of hartree for heavy atoms. The present scheme was found to reproduce the energetics in the four-component treatment with high accuracy.

Divide-and-conquer-type density-functional tight-binding simulations of hydroxide ion diffusion in bulk water

Sakti, Aditya Wibawa; Nishimura, Yoshifumi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Physical Chemistry B 121(6) p.1362 - 13712017/01-2017/01

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ISSN:15206106

Outline:© 2017 American Chemical Society. The diffusion of the hydroxide ion in bulk water was examined by linear-scaling divide-and-conquer density-functional tight-binding molecular dynamics (DC-DFTB-MD) simulations using three different-sized unit cells that contained 522, 1050, and 4999 water molecules as well as one hydroxide ion. The repulsive potential for the oxygen-oxygen pair was improved by iterative Boltzmann inversion, which adjusted the radial distribution function of DFTB-MD simulations to that of the reference density functional theory-MD one. The calculated diffusion coefficients and the Arrhenius diffusion barrier were in good agreement with experimental results. The results of the hydroxide ion coordination number distribution and potential of mean force analyses supported a dynamical hypercoordination diffusion mechanism. (Graph Presented).

Density Functional Theory Analysis of Elementary Reactions in NOxReduction on Rh Surfaces and Rh Clusters

Deushi, Fumiko; Ishikawa, Atsushi; Ishikawa, Atsushi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Physical Chemistry C 121(28) p.15272 - 152812017/07-2017/07

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ISSN:19327447

Outline:© 2017 American Chemical Society. The reduction of NO x is crucial for reducing air pollution from vehicle exhaust. In the presence of Rh-based catalysts, the dissociation of NO and the formation of N 2 O and N 2 constitute the important elementary steps of NO x reduction. The present study used density functional theory (DFT) to investigate the catalytic performances of the Rh(111) surface and Rh 55 and Rh 147 clusters toward these elementary reactions. The NO dissociation reaction was found to have minimum activation barriers (E a ) of 0.63, 0.68, and 1.25 eV on Rh 55 , Rh 147 , and Rh(111), respectively. Therefore, it is the fastest on small Rh clusters. In contrast, the N 2 formation reaction is relatively inefficient on small clusters, with corresponding E a values of 2.14, 1.79, and 1.71 eV. Because of the stronger binding of N atoms to the Rh clusters than to the Rh surface, N 2 formation through the recombination of N atoms has a higher E a value on Rh clusters. The calculated reaction rate constants confirmed that small Rh clusters are less reactive for N 2 formation than Rh(111), especially at low temperatures. Our results also suggest that N 2 O formation is largely endothermic and, thus, thermodynamically unfavored. (Figure Presented).

Computerized implementation of higher-order electron-correlation methods and their linear-scaling divide-and-conquer extensions

Nakano, Masahiko; Yoshikawa, Takeshi; Hirata, So; Hirata, So; Seino, Junji; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Computational Chemistry 38(29) p.2520 - 25272017/11-2017/11

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ISSN:01928651

Outline:© 2017 Wiley Periodicals, Inc. We have implemented a linear-scaling divide-and-conquer (DC)-based higher-order coupled-cluster (CC) and Møller–Plesset perturbation theories (MPPT) as well as their combinations automatically by means of the tensor contraction engine, which is a computerized symbolic algebra system. The DC-based energy expressions of the standard CC and MPPT methods and the CC methods augmented with a perturbation correction were proposed for up to high excitation orders [e.g., CCSDTQ, MP4, and CCSD(2) TQ ]. The numerical assessment for hydrogen halide chains, polyene chains, and first coordination sphere (C1) model of photoactive yellow protein has revealed that the DC-based correlation methods provide reliable correlation energies with significantly less computational cost than that of the conventional implementations. © 2017 Wiley Periodicals, Inc.

Parallel implementation of efficient charge–charge interaction evaluation scheme in periodic divide-and-conquer density-functional tight-binding calculations

Nishimura, Yoshifumi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Computational Chemistry 39(2) p.105 - 1162018/01-2018/01

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ISSN:01928651

Outline:© 2017 Wiley Periodicals, Inc. A low-computational-cost algorithm and its parallel implementation for periodic divide-and-conquer density-functional tight-binding (DC-DFTB) calculations are presented. The developed algorithm enables rapid computation of the interaction between atomic partial charges, which is the bottleneck for applications to large systems, by means of multipole- and interpolation-based approaches for long- and short-range contributions. The numerical errors of energy and forces with respect to the conventional Ewald-based technique can be under the control of the multipole expansion order, level of unit cell replication, and interpolation grid size. The parallel performance of four different evaluation schemes combining previous approaches and the proposed one are assessed using test calculations of a cubic water box on the K computer. The largest benchmark system consisted of 3,295,500 atoms. DC-DFTB energy and forces for this system were obtained in only a few minutes when the proposed algorithm was activated and parallelized over 16,000 nodes in the K computer. The high performance using a single node workstation was also confirmed. In addition to liquid water systems, the feasibility of the present method was examined by testing solid systems such as diamond form of carbon, face-centered cubic form of copper, and rock salt form of sodium chloride. © 2017 Wiley Periodicals, Inc.

Catalytic performance of Ru, Os, and Rh nanoparticles for ammonia synthesis: A density functional theory analysis

Ishikawa, Atsushi; Ishikawa, Atsushi; Ishikawa, Atsushi; Ishikawa, Atsushi; Doi, Toshiki; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Catalysis 357p.213 - 2222018/01-2018/01

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ISSN:00219517

Outline:© 2017 Elsevier Inc. NH 3 synthesis on Ru, Os, and Rh nanoparticle catalysts was investigated using density functional theory calculations. The Ru and Os nanoparticles exhibited similar shapes, while that of Rh differed significantly. For all metal species, step sites appeared at nanoparticle diameters (d) > 2–4 nm. The calculated activation barriers (E a ) were small at step sites, and Ru and Os step sites exhibited similar E a values despite the former having a higher turnover frequency. This is likely due to the surface coverage of vacant sites being higher on Ru. Although the increase in NH 3 synthesis rate at d = 2–4 nm was common to Ru, Os, and Rh, the reaction rates decreased in the order: Ru > Os > Rh. Our results show that E a values, surface vacant sites, and the number of step sites are important factors for NH 3 synthesis. The Ru nanoparticles exhibited high activity due to satisfying all three factors.

Density-Functional Tight-Binding Molecular Dynamics Simulations of Excess Proton Diffusion in Ice Ih, Ice Ic, Ice III, and Melted Ice VI Phases

Sakti, Aditya Wibawa; Nishimura, Yoshifumi; Chou, Chien Pin; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Physical Chemistry A 122(1) p.33 - 402018/01-2018/01

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ISSN:10895639

Outline:© 2017 American Chemical Society. The structural, dynamical, and energetic properties of the excess proton in ice were studied using density-functional tight-binding molecular dynamics simulations. The ice systems investigated herein consisted of low-density hexagonal and cubic crystalline variants (ice I h and I c ) and high-density structures (ice III and melted ice VI). Analysis of the temperature dependence of radial distribution function and bond order parameters served to characterize the distribution and configuration of hundreds of water molecules in a unit cell. We confirmed that ice I h and I c possess higher hexagonal symmetries than ice III and melted ice VI. The estimated Grotthuss shuttling diffusion coefficients in ice were larger than that of liquid water, indicating a slower proton diffusion process in high-density structures than in low-density systems. The energy barriers calculated on the basis of the Arrhenius plot of diffusion coefficients were in reasonable agreement with experimental measurement for ice I h . Furthermore, the energy barriers for high-density structures were several times larger than those of low-density systems. The simulation results were likely related to the suppression of proton transfer in disordered water configurations, in particular, ice with low hexagonal symmetry.

Rigorous pKaEstimation of Amine Species Using Density-Functional Tight-Binding-Based Metadynamics Simulations

Sakti, Aditya Wibawa; Nishimura, Yoshifumi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi; Nakai, Hiromi

Journal of Chemical Theory and Computation 14(1) p.351 - 3562018/01-2018/01

DOIScopus

Detail

ISSN:15499618

Outline:© 2017 American Chemical Society. Predicting pK a values for different types of amine species with high accuracy and efficiency is of critical importance for the design of high performance and economical solvents in carbon capture and storage with aqueous amine solutions. In this study, we demonstrate that density-functional tight-binding-based metadynamics simulations are a promising approach to calculate the free energy difference between the protonated and neutral states of amines in aqueous solution with inexpensive computational cost. The calculated pK a values were in satisfactory agreement with the experimental values, the mean absolute deviation being only 0.09 pK a units for 34 amines commonly used in CO 2 scrubbing. Such superior reproducibility and correlation compared to estimations by static quantum mechanical calculations highlight the significant effect of dynamical proton transfer processes in explicit solvent molecules for the improvement of the estimation accuracy.

Electron-Hopping Brings Lattice Strain and High Catalytic Activity in the Low-Temperature Oxidative Coupling of Methane in an Electric Field

Ogo, Shuhei; Ogo, Shuhei; Nakatsubo, Hideaki; Iwasaki, Kousei; Sato, Ayaka; Murakami, Kota; Yabe, Tomohiro; Ishikawa, Atsushi; Ishikawa, Atsushi; Ishikawa, Atsushi; Nakai, Hiromi; Sekine, Yasushi

Journal of Physical Chemistry C 122(4) p.2089 - 20962018/02-2018/02

DOIScopus

Detail

ISSN:19327447

Outline:© 2018 American Chemical Society. Detailed reaction mechanisms for the oxidative coupling of methane (OCM) over Ce 2 (WO 4 ) 3 catalysts at low temperatures in an electric field were investigated. The influence of Ce cations in the Ce 2 (WO 4 ) 3 catalyst was evaluated by comparing the OCM activity over various Ln 2 (WO 4 ) 3 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) catalysts in an electric field. The electronic states of Ln and W cations and the relationship between the distorted Ce 2 (WO 4 ) 3 structure and methane activation were examined using X-ray absorption fine structure (XAFS) measurements and first-principles calculations. The results reveal that the Ln 2 (WO 4 ) 3 catalysts with redox-active Ln cations (Ce, Pr, Sm, Eu, and Tb) show OCM activity. First-principles calculations indicate that Ce 3+ species in the Ce 2 (WO 4 ) 3 structure are oxidized to Ce 4+ species in an electric field by extracting electrons from the Ce 4f orbitals near the Fermi level; as a result, its structure is distorted. The results indicate that the redox reaction of Ln cations in Ln 2 (WO 4 ) 3 induced by an electric field brings lattice strain and a high OCM activity in an electric field.

Local Response Dispersion Method in Periodic Systems: Implementation and Assessment

Ikabata, Yasuhiro;Tsukamoto, Yusuke;Imamura, Yutaka;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 36(5) p.303 - 3112015-2015

DOIWoS

Detail

ISSN:0192-8651

Quantum chemical approach for condensed-phase thermochemistry (II): Applications to formation and combustion reactions of liquid organic molecules

Ishikawa, Atsushi;Nakai, Hiromi

CHEMICAL PHYSICS LETTERS 624p.6 - 112015-2015

DOIWoS

Detail

ISSN:0009-2614

Revisiting the Extrapolation of Correlation Energies to Complete Basis Set Limit

Okoshi, Masaki;Atsumi, Teruo;Nakai, Hiromi

JOURNAL OF COMPUTATIONAL CHEMISTRY 36(14) p.1075 - 10822015-2015

DOIWoS

Detail

ISSN:0192-8651

Accompanying coordinate expansion and recurrence relation method using a transfer relation scheme for electron repulsion integrals with high angular momenta and long contractions

Hayami, Masao;Seino, Junji;Nakai, Hiromi

JOURNAL OF CHEMICAL PHYSICS 142(20) 2015-2015

DOIWoS

Detail

ISSN:0021-9606

Theoretical Analysis of the Oxidation Potentials of Organic Electrolyte Solvents

Okoshi, Masaki;Ishikawa, Atsushi;Kawamura, Yoshiumi;Nakai, Hiromi

ECS ELECTROCHEMISTRY LETTERS 4(9) p.A103 - A1052015-2015

DOIWoS

Detail

ISSN:2162-8726

Quantum Chemical Simulations for Atoms and Molecules

Nakai Hiromi;Okoshi Masaki

Journal of the Japan Society for Simulation Technology 30(4) p.199 - 2062011/12-2011/12

CiNii

Detail

ISSN:02859947

Discovery of Chemical Principles:Symmetry Rules for Degenerate Excitations

NAKAI Hiromi

Journal of Chemical Software 11(1) p.1 - 162012-2012

CiNii

Detail

ISSN:1347-1767

Outline:The article discusses chemical principles such as concept, theorem, rule, and hypothesis, which fulfil the role of so-called milestone in the chemical researches. After overviewing the history of quantum chemistry, the author would like to raise the issue how modern-day theoretical chemists should confront the chemical principles. Next, the symmetry rules for degenerate excitations, which are the chemical principles discovered by the authors group, are described. In particular, this article explains the background of the discovery, the verification by the numerical assessments, and the theoretical interpretation.

Large-Scale and Highly Accurate Relativistic Quantum-Chemical Scheme:toward Establishment ofTheoretical Foundation for Element Strategy

SEINO Junji;NAKAI Hiromi

Journal of Chemical Software 13(1) p.1 - 172014-2014

CiNii

Detail

ISSN:1347-1767

Outline:The article discusses a highly efficient and accurate theory for electronic-state calculations of large-scale heavy-element compounds. After overviewing the current relativistic quantum-chemical theories, the authors describe what points should be considered and improved in order to attain the objective. In addition, they have developed an efficient and accurate two-component relativistic scheme, termed local unitary transformation (LUT) scheme based on infinite-order Douglas-Kroll-Hess method. Numerical applications show the effectiveness of the scheme. Furthermore, the extension of the LUT scheme to the divide-and-conquer (DC) method achieves overall linear-scaling computational cost. In particular, the present scheme would realize a paradigm shift from a non-relativistic (NR) framework to a relativistic one in the quantum chemistry field because the scheme gives close results to four-component relativistic ones with NR computational costs.

Theoretical Study on the Selective Fluorescence of PicoGreen: Binding Models and Photophysical Properties

Okoshi Masaki;Saparpakorn Patchreenart;Takada Yuta;Hannongbua Supa;Nakai Hiromi

Bull. Chem. Soc. Jpn. 87(2) p.267 - 2732014-2014

CiNii

Detail

ISSN:0009-2673

Outline:PicoGreen (PG) is used as a probe to selectively quantitate double-stranded (ds-) DNA because it shows unique fluorescence enhancement when complexed with DNA. By binding to ds- and single-stranded (ss-) DNA, the quantum yields of PG–DNA complexes become remarkably larger than that of a free molecule. In the present theoretical study, the fluorescence enhancement mechanism of PG–DNA complexes was investigated using molecular docking simulations and ab initio quantum chemical methods. The binding energies between PG and ds-DNA were calculated to be larger than those in the case of PG and ss-DNA owing to the existence of an extra π–π stacking interaction. Nonradiative deactivation paths through conical intersections between the ground and the first excited states were obtained for a free PG molecule, while steric repulsions between PG and DNA hindered such deactivation processes in the case of PG–DNA complexes.

Theoretical Study on Excess-Electron Transfer in DNA Based on the Marcus Theory

TAKADA Yuta;OKOSHI Masaki;HOSHINO Minoru;ISHIKAWA Atsushi;ISIKAWA Makoto;NAKAI Hiromi

Journal of Chemical Software 13(4) p.242 - 2492014-2014

CiNii

Detail

ISSN:1347-1767

Outline:DNAs, which have charge transport abilities, are expected to apply to advanced materials in nanotechnology as conducting nano-wires. While the hole-transfer in DNA has been extensively investigated in many experimental and theoretical studies, the knowledge on the transfer of a negative charge, i.e., the excess-electron transfer (EET), is limited so far. In the present study, we evaluated the rate constants of EET in DNA, using the Marcus theory with density functional theory (DFT) calculations. The computed rate constant of EET between thymine bases, 2.31 − 3.49 × 1010 s−1, showed good agreement with the experimental value, 4.4 ± 0.3 × 1010 s−1. Furthermore, the mechanism of the decrease of EET rates due to miss-match base pairs was elucidated.

Books And Publication

化学ってそういうこと!ー夢が広がる分子の世界ー

化学同人社2003/01-2003/01

Meso-scale Quantum Chemistry

H. Nakai, Y. Imamura, Y. Kikuchi, M. Kobayashi, T. Akama, J. Seino

Meso???2012/01-2012/01

Description of Core Ionized and Excited States by Density Functional Theory and Time-dependent Density Functional Theory

Y. Imamura, H. Nakai

Advances in the Theory of Atomic and Molecular Systems2012/04-2012/04

化学原理の発見:縮重系励起の対称則

H. Nakai

J. Comput. Chem. Jpn.2012/04-2012/04

How does it become possible to treat delocalized and/or open-shell systems in fragmentation-based linear-scaling electronic structure calculation: the case of divide-and-conquer method

M. Kobayashi, H. Nakai

Phys. Chem. Chem. Phys.2012/03-2012/06

巨大分子系の量子化学法

中井浩巳

CSJカレントレビュー・シリーズ第8巻「巨大分子系の計算化学-超大型計算機時代の理論化学の新展開」2011/03-2012/03

量子化学に基づく原子・分子のシミュレーション

中井浩巳, 大越昌樹

日本シミュレーション学会誌「シミュレーション」2011/12-2011/12

理論化学における理論の革新

中井浩巳

「化学のブレークスルー」2011/10-2011/10

炭素原子の電子配置

中井浩巳

『炭素学』2011/10-2011/10

ナノ科学のための分割統治量子化学計算法

小林正人,中井浩巳

ナノ学会会報「次世代スパコン特集」2011/03-2011/03

Divide-and-conquer approaches to quantum chemistry: Theory and implementation

M. Kobayashi, H. Nakai

Linear-Scaling Techniques in Computational Chemistry and Physics: Methods and Applications2010/02-2011/02

理論化学における理論の革新

中井浩巳

別冊化学「化学のブレークスルー【理論化学編】」2010/05-2010/05

Rules for excited states of degenerate systems: Interpretation by frozen orbital analysis

H. Nakai

Advances in the Theory of Atomic and Molecular Systems: Conceptual and Computational Advances in Quantum Chemistry’ Progress in Theoretical Chemistry and Physics2009/04-2009/04

化学の領域を広げる巨大分子の電子状態計算

小林正人,中井浩巳

化学2008/11-2009/01

インシリコ・ケミストリー〜高性能量子化学計算環境の構築〜

中井浩巳

早稲田産学連携レビュー20092008/09-2009/09

Development of linear scaling techniques based on divide-and-conquer method

H. Nakai, T. Akama, M. Kobayashi

Bull. Soc. Discrete Variational Xα2008/09-2008/09

メソ物質設計のための線形スケーリング量子化学計算

中井浩巳

化学と工業2008/08-2008/10

エネルギー密度解析による表面モデルの検証および触媒作用の解明

中井浩巳, 菊池那明, 今村穣

触媒2008/07-2008/10

New expression of the chemical bond in hydrides using atomization energies

Y. Shinzato, H. Yukawa, M. Morinaga, T. Baba, H. Nakai

Adv. Quant. Chem.2008/01-2008/01

Nuclear orbital plus molecular orbital (NOMO) theory: Simultaneous determination of nuclear and electronic wave functions without Born-Oppenheimer approximation

H. Nakai

Int. J. Quant. Chem. (Review)2007/03-2007/09

原子核と電子の波動関数を同時に決定するためのnon-Born-Oppenheimer理論:NOMO理論

中井浩巳, 星野稔

Mol. Sci. (分子科学)2007/06-2007/06

表面-分子相互作用系の量子化学計算に関する最近の動向

中井浩巳

表面科学2007/01-2007/03

Energy Density Analysis of Kohn-Sham DFT Method and Its Applications

T. Baba, Y. Yamauchi, Y. Kikuchi, Y. Kurabayashi, H. Nakai

Bull. Soc. Discrete Variational Xα.2005/11-2005/12

化学ってそういうこと!-夢が広がる分子の世界-

中井浩巳, 日本化学会編(共著)

化学同人 2003-2003

表面光化学反応の理論展開

中辻博, 中井浩巳

有機合成化学研究所講演集、第8集1994-1994

固体触媒作用の量子化学

中辻博, 波田雅彦, 中井浩巳, 福西快文

触媒1994-1994

固体表面上での化学吸着と触媒反応の電子論

中辻博, 波田雅彦, 中井浩巳

表面科学1993-1993

Catalytic reactions of transition metal clusters and surfaces from ab initio theory-cluster and dipped adcluster model studies combined with the SAC/SAC-CI method-

H. Nakatsuji, H. Nakai, M. Hada

‘Metal-ligand interctions: from atoms, to clusters, to surfaces’, Ed. D. R. Salahub, NATO ASI Series, Reidel, Dordrecht1992-1992

金属表面における化学吸着と触媒作用

中井浩巳, 福西快文, 中辻博

季刊化学総説1991-1991

触媒作用の量子化学

中辻博, 波田雅彦, 中井浩巳

有機合成化学研究所 講演集1991-1991

Research Grants & Projects

Grant-in-aids for Scientific Research Adoption Situation

Research Classification:

Development of accelerated quantum dynamics theory

Allocation Class:¥19200000

Research Classification:

Innovation of 6 Coordinate Hypervalent Compounds Bearing Carbon and Phosphorus as Central Atoms

Allocation Class:¥3000000

Research Classification:

Time-Resolved Spectroscopy of Photoinduced Molecular Stractural Dynamics

Allocation Class:¥6200000

Research Classification:

Theoretical Study on the Excited Dynamics of Solid Surfaces and Surface Adsorbates

Allocation Class:¥2200000

Research Classification:

Development of the large scale computational program system based on the SAC-CI method

Allocation Class:¥13900000

Research Classification:

Theoretical study on the fundamental electronic process of the surface photochemistry

1993-1995

Allocation Class:¥15400000

Research Classification:

Clarification of Ubiquitous Proton Function in Photoreceptive Proteins by Quantum Molecular Dynamics Simulations

2018/-0-2023/-0

Allocation Class:¥196430000

Research Classification:

Development of Real-Time Formula of Molecular Theory and Its Applications to Nonequilibrium Processes

2010/-0-2013/-0

Allocation Class:¥3510000

On-campus Research System

Special Research Project

実践的インシリコ・ケミストリーの確立:量子化学計算による材料設計に向けて

2010Collaborator:今村 穣, 菊池 那明, 小林 正人, 赤間 知子, 清野 淳司

Research Results Outline:本研究では、大規模系に対する量子化学計算を実行するための理論・計算アルゴリズムの開発とそれらを用いた実践研究を行った。具体的には、(1) 実時間発展形本研究では、大規模系に対する量子化学計算を実行するための理論・計算アルゴリズムの開発とそれらを用いた実践研究を行った。具体的には、(1) 実時間発展形式の時間依存密度汎関数理論(RT-TDDFT)の実装、(2) 構造最適化計算の高速化手法(LSMO...本研究では、大規模系に対する量子化学計算を実行するための理論・計算アルゴリズムの開発とそれらを用いた実践研究を行った。具体的には、(1) 実時間発展形式の時間依存密度汎関数理論(RT-TDDFT)の実装、(2) 構造最適化計算の高速化手法(LSMO)の開発、(3) 分散力を扱うための密度汎関数理論(LRD)の開発、(4) 開殻系に対する分割統治法(DC-UHF/UDFT)の開発である。(1)では、RT-TDDFT法の計算プログラムを実装し、さらに短時間フーリエ変換(STFT)を適用することにより、励起状態におけるエネルギー移動を実時間で解析することに成功した。(2)では、非経験的分子シミュレーションおよび構造最適化計算における自己無撞着場(SCF)計算の収束性を改善する方法としてLSMO法を開発した。これによりAIMD法で約50%、AIMC法で約40%、Opt計算で約20%の高速化に成功した。(3)では、DFT法の欠点である弱い相互作用を記述できる第一原理的手法を開発し、実験で観測されるC6係数を高精度に再現することが確かめられた。(4)では、開殻系に適用できるO(N)法としてDC-UHF/UDFT法を開発し、非局在化スピンを含む系にも適用できることを確かめた。

インシリコ元素戦略に向けた相対論的量子化学理論の構築と実践

2012

Research Results Outline: 本特定課題研究Bでは、元素戦略に必要な相対論的量子化学理論の構築を目指した。特に理論的な基盤となる次の2点を実施した。(1)局所ユニタリー変換(LU 本特定課題研究Bでは、元素戦略に必要な相対論的量子化学理論の構築を目指した。特に理論的な基盤となる次の2点を実施した。(1)局所ユニタリー変換(LUT)法による2成分相対論法の高速化(2)一般化非制限ハートリー・フォック(GUHF)法及びその電子... 本特定課題研究Bでは、元素戦略に必要な相対論的量子化学理論の構築を目指した。特に理論的な基盤となる次の2点を実施した。(1)局所ユニタリー変換(LUT)法による2成分相対論法の高速化(2)一般化非制限ハートリー・フォック(GUHF)法及びその電子相関理論(GUMP2)の確立。テーマ(1)では、周期表のあらゆる元素を含む物質・材料に対して、確証性の高い特性評価・機能設計を可能とするための相対論的量子化学理論の基盤構築を目指した。特に、2成分相対論法のうちで最も高精度な無限次ダグラス・クロール変換(IODK/IODK)法を基礎として、その弱点である莫大な計算コストを軽減するために局所ユニタリー変換(LUT)法を開発した。これにより、計算時間における線形スケーリング(計算時間が系の大きさに比例)および化学的精度(1 kcal/mol)を保った計算誤差が示され、本手法の有用性が確認された。テーマ(2)では、スピン依存部分を含むハミルトニアンでは様々な形式のスピン演算子が含まれることから、これらの形式に対応可能なGUHF法及びGUMP2を確立した。簡単な分子で数値検証を行った結果、従来の2成分相対論法では電子相関エネルギーを過剰評価する傾向があるが、本手法では4成分相対論法とほぼ同様の結果を与えることが確認された。これにより、電子相関効果と相対論効果を同時にしかも高精度に取り扱えるようになった。 本特定課題研究Bは、平成24年度科学研究費補助金基盤研究(A)(申請49,810千円)に不採択を受けて、平成25年度の再申請につなげるための研究費という位置づけであった。しかし、本研究代表者はさらなるステップアップを目指して、上記のような理論基盤を充実させたのち、科学技術振興機構(JST)が募集する戦略的創造研究推進事業(CREST)「元素戦略を基軸とする物質・材料の革新的機能の創出」に応募し、採択に至った。チーム全体の研究経費も290,000千円(うち研究代表者の研究経費は140,000千円)である。研究課題名も、本特定課題をさらに発展させた「相対論的電子論が拓く革新的機能材料設計」というものとした。

大規模量子科学計算と分子動力学法の融合による化学反応シミュレーションの実行

2013

Research Results Outline:本研究の目的は,申請者らがこれまでに開発・発展させてきた大規模量子化学計算である分割統治(DC)法に分子動力学(MD)法を組み合わせることにより,結合本研究の目的は,申請者らがこれまでに開発・発展させてきた大規模量子化学計算である分割統治(DC)法に分子動力学(MD)法を組み合わせることにより,結合の生成・開裂を伴う化学反応の動的なシミュレーションを行うことである。これにより,従来の量子化学計算...本研究の目的は,申請者らがこれまでに開発・発展させてきた大規模量子化学計算である分割統治(DC)法に分子動力学(MD)法を組み合わせることにより,結合の生成・開裂を伴う化学反応の動的なシミュレーションを行うことである。これにより,従来の量子化学計算だけでは困難であった温度や時間の効果を取り込むこと、従来のMD法では困難であった結合の生成・開裂を取り扱うことの克服を目指した。原理的には単に量子化学計算とMD法を組み合わせるだけ(一般にAIMD法と呼ばれる)で化学反応シミュレーションは行えるが,MD法の時間ステップ(通常,1フェムト秒(fs)程度)ごとに量子化学計算,特に,力の計算を行う必要があり,現実的な反応を追跡できない。本研究では,比較的計算コストが小さい密度汎関数強束縛(DFTB)法に着目し,さらにDC法を適用することにより,この困難を克服した。また、「京」コンピュータなどの超並列環境に対応したプログラム開発も行った。8,000分子の水に対するDC-DFTB法のエネルギー計算が,2,500ノード(20,000コア)を使用することにより1.125秒で実行できることを確かめた。並列化度79.5%に加えて、高い実行効率も達成した。さらに、(1)アミン溶液によるCO2吸収・放散過程,(2)グラファイト電極表面での電解質溶液の分解反応,という2つの化学反応に応用した。(1)では、CO2の吸収過程では、OH-によるプロトンの引き抜きが水の水素結合ネットワークを介してアミン-CO2複合系に作用することを明らかにした。一方、放散過程では、カルバメートとプロトン化アミンが直接プロトンの授受を行っていることを明らかにした。このように、同一の反応であっても、微視的な反応機構が異なることは、反応シミュレーションによって初めて明らかにできることであり、本研究の意義は大きい。(2)では、実験的にとらえることが困難なSEI膜の成長過程の初期段階を明らかにした。

相対論的量子化学とインフォマティクスによる均一系触媒を用いた反応予測手法の開発

2017Collaborator:清野 淳司

Research Results Outline:本研究では、(A)機械学習や群知能などの人工知能技術を用いて相対論的量子化学計算法の高精度化を目指した。また、(B)相対論的量子化学計算の結果を用いた本研究では、(A)機械学習や群知能などの人工知能技術を用いて相対論的量子化学計算法の高精度化を目指した。また、(B)相対論的量子化学計算の結果を用いた反応予測システムの開発を目指した。テーマ(A)では、密度汎関数理論の肝となる汎関数を群知能および機...本研究では、(A)機械学習や群知能などの人工知能技術を用いて相対論的量子化学計算法の高精度化を目指した。また、(B)相対論的量子化学計算の結果を用いた反応予測システムの開発を目指した。テーマ(A)では、密度汎関数理論の肝となる汎関数を群知能および機械学習により決定することに成功した。また、相対論的密度汎関数理論では、4成分法から2成分法に描像を変化させる場合、電子密度の見積りに注意が必要であり、そのための処方を示すことができた。テーマ(B)では、機械学習により量子化学的記述子を用いた反応予測システムの開発に成功した。

金属錯体の励起状態と光化学反応に関する理論的研究

1996

Research Results Outline: 本研究では、金属錯体の励起状態の量子化学計算から、それらを一般的に理解するための規則を見い出すことに成功した。また、励起状態のポテンシャル面の計算か 本研究では、金属錯体の励起状態の量子化学計算から、それらを一般的に理解するための規則を見い出すことに成功した。また、励起状態のポテンシャル面の計算から、Mo(CO)6の光分解反応や白金テトラシアノエチレン錯体の光異性化反応の電子的メカニズムを解明... 本研究では、金属錯体の励起状態の量子化学計算から、それらを一般的に理解するための規則を見い出すことに成功した。また、励起状態のポテンシャル面の計算から、Mo(CO)6の光分解反応や白金テトラシアノエチレン錯体の光異性化反応の電子的メカニズムを解明した。ここでは、前者の研究について、その概要を報告する。 金属錯体の励起状態に関する一般則:多くの金属錯体は高い対称性を持つため、二重あるいは三重に縮退した分子軌道を持つ。それらの縮退軌道間の遷移に基づく励起状態は、複数個現われる。我々は、これら励起状態の順序や分裂幅には、一般則があることを見い出した。すなわち、「同じ主配置を持つ複数の励起状態のうち、許容遷移に相当する状態は最も高いエネルギー準位に位置し、しかも他の準位との分裂幅も最も大きい。」実際に我々は、この規則が、正四面体(Td)構造のオキソ錯体、MO4(M=Cr,Mo,Mn,Tc,Ru,Os)、正八面体(Oh)構造のMoF6やMo(CO)6などについて成り立つことを確認した。さらに、この規則は金属錯体に限らず、縮退軌道間の遷移に基づく励起状態に関する一般則であることも確認した。例えば、直線分子やD6h構造のベンゼンのpai-pai*励起状態、正20面体構造のC60やB12H122-の励起状態などである。このように、この規則が任意の分子について成り立つのは、エネルギー準位や分裂幅が分子の性質には関係なく、遷移に関係する分子軌道の重なりにのみ依存しているためである。さらに、この規則は、ちょうどHund則が同じ主配置を持つ異なるスピン状態に関するものであるのに対し、同じスピン状態内で成り立つ規則として注目に値する。

金属錯体の励起ダイナミックスと光触媒作用に関する理論的研究

1997

Research Results Outline:本研究では、励起ダイナミックスおよび触媒反応の電子過程を明らかにすることを目的とした。以下に具体的な研究成果を報告する。 1.Cu/ZnO触媒によるメ本研究では、励起ダイナミックスおよび触媒反応の電子過程を明らかにすることを目的とした。以下に具体的な研究成果を報告する。 1.Cu/ZnO触媒によるメタノール合成反応:本研究では、清浄表面(Cu4)および亜鉛蒸着表面(Cu3Zn)上でCO2とH2か...本研究では、励起ダイナミックスおよび触媒反応の電子過程を明らかにすることを目的とした。以下に具体的な研究成果を報告する。 1.Cu/ZnO触媒によるメタノール合成反応:本研究では、清浄表面(Cu4)および亜鉛蒸着表面(Cu3Zn)上でCO2とH2からメタノールを生成する反応について理論的に調べた。その結果、 Zn-Cuに橋掛けしたフォーメート中間体の存在が確認され、安定性・反応性ともに清浄表面のものよりも有利であることがわかった。吸着フォーメートの水素化反応過程では、ジオキソメチレン中間体、メトキシ中間体を経て、メタノールが生成することがわかった。Cu表面の触媒作用やZnの助触媒効果には、種々の吸着種への多彩な電子移動が密接に関与していることが明らかとなった。 2.[V4O12]4-担持アリル-ロジウム錯体によるC-Cカップリング反応:本研究では、アリル-ロジウム錯体がC-Cカップリング反応を起してヘキサジエンを生成する過程を理論的に調べた。その結果、C-Cカップリング反応のエネルギー障壁は、アセチルアセトナート上に担持されたものに比べて、分子性酸化物[V4O12]4-上では半分程度であった。この違いは、ロジウム錯体部位への電子移動の違いに由来しており、次のような構造変化とも関係している。フリーな [V4O12]4-では、V4O4という8員環はπ共役により平面構造を有しているが、ロジウム錯体がこれに配位すると平面構造は崩れる。この崩れによりπ電子が局在化され、ロジウム錯体部位への電子移動を容易にしているのである。また、2個のロジウム錯体が配位する場合、V4O4の8員環を通した長距離相互作用によりC-Cカップリング反応をサポートしていることも明らかとなった。研究成果の発表:[1] Mechanism of the Partial Oxidation of Ethylene on an Ag Surface:Dipped Adcluster Model Study, H. Nakatsuji, H. Nakai, K. Ikeda, and Y.Yamamoto, Surf. Sci., 384, 315-333 (1997). [2] Activation of O2 on Cu, Ag, and Au Surfaces for the Epoxidation of Ethylene: Dipped Adcluster Model Study, H. Nakatsuji, Z. Hu, H. Nakai, and K. Ikeda, Surf. Sci., 387, 328-341 (1997). [3] Theoretical Study on the Catalytic Activity of Ag Surface for the Oxidation of Olefins, H. Nakatsuji, Z.M. Hu, and H. Nakai, Int. J. Quant. Chem., 65, 839-855 (1997). [4] Electronic Structures of the Ground and Excited States of Mo(CO)6:SAC-CI Calculation and Frozen Orbital Analysis, H. Morita, H. Nakai, H. Hanada, and H. Nakatsuji, Mol. Phys., 92 (3), 523-534 (1997). [5] Electronic Structures of the Ground and Excited States of MoF6 and MoOF4: SAC-CI Calculation and Frozen Orbital Analysis, H. Nakai, H. Morita, P. Tomasello, and H. Nakatsuji, J. Phys. Chem., in press (1998).

多次元プロトン・トンネリングのメカニズムに関する理論的研究

1998

Research Results Outline: 本研究では、多自由度のプロトン・トンネリングが関係する系に対して、理論的なアプローチにより、そのメカニズムの解明を行った。具体的には、(1)置換ト 本研究では、多自由度のプロトン・トンネリングが関係する系に対して、理論的なアプローチにより、そのメカニズムの解明を行った。具体的には、(1)置換トルエンにおける励起状態のメチル基回転障壁、(2)マロンアルデヒドにおけるプロトン・トンネリング分裂... 本研究では、多自由度のプロトン・トンネリングが関係する系に対して、理論的なアプローチにより、そのメカニズムの解明を行った。具体的には、(1)置換トルエンにおける励起状態のメチル基回転障壁、(2)マロンアルデヒドにおけるプロトン・トンネリング分裂、について研究を行った。(1)では、基底(S0)および励起(S1)状態にある置換トルエンのメチル基分子内回転に対するポテンシャルカーブを分子軌道(MO)計算により求め、実験的に観測されているようなS0→S1励起に伴う回転障壁の劇的な変化を理論的に再現した。計算結果の解析より、この劇的な変化はLUMOにおける新しいタイプの超共役が原因であることが示された。このメカニズムによると、これまで明らかにされなかった置換基の位置や種類による回転障壁の変化も矛盾なく説明できることもわかった。(2)では、多自由度のプロトン・トンネリングを取り扱えるようにするために、従来のMO法に替わるNO+MO法を提案し、その理論に基づいた計算プログラムの開発を行った。本研究では、このNO+MO法を適用することにより、マロンアルデヒドのトンネリング分裂幅を理論的に予測することに成功した。特に、重水素置換することで分裂幅が1オーダー減少することが報告されているが、理論的にもこのことが再現された。また、より多くの分子をこのNO+MO法で取り扱えるように、原子核の波動関数(NO)を記述するための基底関数の開発も同時に行った。

ヘテロバイメタリッククラスターの触媒作用に関する理論的研究

2000

Research Results Outline: 本研究では、固体表面および金属錯体の関与する反応に対して、その触媒作用のメカニズムを理論的に解明することを目指した。固体表面に対しては、クラスターモ 本研究では、固体表面および金属錯体の関与する反応に対して、その触媒作用のメカニズムを理論的に解明することを目指した。固体表面に対しては、クラスターモデルによる取り扱いで問題となる、クラスターサイズ依存性に関して系統的に調べた。その結果、吸着分子の... 本研究では、固体表面および金属錯体の関与する反応に対して、その触媒作用のメカニズムを理論的に解明することを目指した。固体表面に対しては、クラスターモデルによる取り扱いで問題となる、クラスターサイズ依存性に関して系統的に調べた。その結果、吸着分子の構造や振動数などは金属原子数個のクラスターを用いた計算でも収束しているが、生成熱などエネルギーは40個のクラスターを用いても収束が見られない、という興味深い結果が得られた。その原因として、クラスターを切り出したことによる不安定性が直接エネルギー計算に影響していることが示された。具体的な触媒反応としては、銅表面におけるメタノール合成を取り上げ、吸着活性種の特定、反応経路の決定、銅の触媒作用、蒸着亜鉛の助触媒効果などを検討した。特に本年度は、律速段階であるフォーメートからジオキソメチレンに至る過程を重点的に調べ、一般にその特定が困難とされる固体表面反応の遷移状態を理論的に求めることに成功した。金属錯体の関与する反応としては、Ru(II)-Sn(II)複核錯体における酢酸合成反応を検討した。本研究を通して、異種金属間結合が触媒反応に果たす多種多様な機能の解明に、理論的にはどのようなアプローチが可能かを検討することができた。

電極表面反応の理論設計

2000

Research Results Outline: 本研究では、(1)電極表面のSTMシミュレーションを行い、正しい理解を理論的に与えること、(2)電極表面で起こる触媒反応と電子移動を理論計算により検 本研究では、(1)電極表面のSTMシミュレーションを行い、正しい理解を理論的に与えること、(2)電極表面で起こる触媒反応と電子移動を理論計算により検討し、そのメカニズムの解明を目指した。テーマ(1)として、Au(111)面に吸着したSulfate... 本研究では、(1)電極表面のSTMシミュレーションを行い、正しい理解を理論的に与えること、(2)電極表面で起こる触媒反応と電子移動を理論計算により検討し、そのメカニズムの解明を目指した。テーマ(1)として、Au(111)面に吸着したSulfateに対して、吸着構造とそのSTM像を理論計算により決定することを試みた。吸着構造はon-top-site eclipse型<hollow-site staggered型<hollow-site eclipse型という順に安定となることがわかった。この結論は、OsawaらのSEIRASの結果とも一致している。さらに、eclipse型吸着構造についてSTM像について検討した。吸着SulfateのバンドはFermi準位付近には現われていないため、通常考えられているTipと吸着系の間のHOMO-LUMO遷移では吸着Sulfateの像は得られない。しかし、電極表面特有の遷移を考えることにより、吸着SulfateのSTM像の再現に成功した。テーマ(2)として、無電解鍍金における還元剤の酸化反応メカニズムについて検討した。その結果、ジメチルアミンボランや次亜リン酸などの還元剤については、これまで広く受け入れられてきた脱水素が先行し3配位化合物を経由するというMeerakker機構よりも、水酸基の配位が先行し5配位化合物を経由するという新たな反応機構が理論的に支持された。溶媒効果を考慮した計算結果から、還元剤が極性溶媒中では自発的に酸化されないが、バルク溶液に比べ誘電率が小さい電気二重層中では酸化されやすくなっていることが示された。さらに、析出金属の自己触媒作用により還元剤の酸化が起こりやすいことが理論的に示された。

クラスター内部自由度の理論的評価に基づく反応設計

2002

Research Results Outline:本研究では、衝突や励起によって引き起こされるクラスター内部自由度の変化を理論的に評価することにより、それに伴う化学反応を解明・予測・設計することを目指本研究では、衝突や励起によって引き起こされるクラスター内部自由度の変化を理論的に評価することにより、それに伴う化学反応を解明・予測・設計することを目指した。具体的には、(1)アンモニアクラスターイオンの衝突反応と(2)ソラレン化合物のDNA光付加反...本研究では、衝突や励起によって引き起こされるクラスター内部自由度の変化を理論的に評価することにより、それに伴う化学反応を解明・予測・設計することを目指した。具体的には、(1)アンモニアクラスターイオンの衝突反応と(2)ソラレン化合物のDNA光付加反応を検討した。(1)については、理研のグループにより、サイズ選別したアンモニアクラスターイオンと重水素化したアンモニアモノマーの衝突実験が報告されている。さらに、吸着および分解過程に対する反応断面積の衝突エネルギーおよびクラスターサイズ依存性も報告されている。そこで本研究では、衝突過程のAb Initio Molecular Dynamics (AIMD)シミュレーションを行い、その結果から分子衝突と化学反応性の関連を検討した。衝突反応の初期条件を変化させたトラジェクトリーを走らせ、その結果から吸着・分解・非反応性衝突・非衝突を判断した。この結果を統計処理することにより得られた反応断面積は、まずまず実験値を再現した。さらに、吸着と分解を導く場合では、衝突サイトには系統的な違いがあることが初めて示された。(2)では、乾癬などの皮膚病に対する光療法の薬として用いられるソラレン化合物を扱った。ソラレン化合物単体での励起状態ダイナミックスを調べる目的で、励起三重項状態におけるAIMDシミュレーションを行った。その結果、無置換ソラレンや5-メトキシソラレン(5-MOP)には見られなかったピロン環の開環が、8-メトキシソラレン(8-MOP)で起こることが初めて明らかとなった。この開環構造は、DNAにフラン環側で付加した場合にも見られ、2段階目の付加反応が抑制されていることがわかる。実際、DNAへのモノ付加体は治療効果があるが、ジ付加体は結合が強固なためDNAが再生されにくく副作用があると考えられている。本研究の結果を踏まえると、8-MOPは副作用という点では最も優れた薬であると判断される。

酸化チタン表面上での光エネルギー変換及び光触媒作用の電子的機構に関する理論的研究

2005

Research Results Outline:本特定課題研究では、酸化チタン表面上での光エネルギー変換及び光触媒作用の本質を分子軌道(MO)法や密度汎関数理論(DFT)などの第一原理計算手法により本特定課題研究では、酸化チタン表面上での光エネルギー変換及び光触媒作用の本質を分子軌道(MO)法や密度汎関数理論(DFT)などの第一原理計算手法により解明することを目指した。具体的には、 (1) 修飾された酸化チタン表面の幾何構造及び電子状態、およ...本特定課題研究では、酸化チタン表面上での光エネルギー変換及び光触媒作用の本質を分子軌道(MO)法や密度汎関数理論(DFT)などの第一原理計算手法により解明することを目指した。具体的には、 (1) 修飾された酸化チタン表面の幾何構造及び電子状態、および(2) 酸化チタン表面における光分解反応、を検討課題とした。研究テーマ(1)では、ガウス基底を用いた周期境界条件(PBC)計算によって天然に存在する酸化チタンが持つ3つの結晶構造(ルチル、アナターゼ、ブルッカイト)に電子状態を検討した。特に、各結晶構造に対してそれぞれ3種類の表面構造のPBC計算を行った。特に、これらの理論的解析において、我々が独自に開発したエネルギー密度解析(EDA)をPBC計算と組み合わせること(PBC-EDA)で、表面とバルクの違い、結晶構造および結晶表面の違いによる安定性や反応性の違いを定量的に評価することに成功した。また、酸化チタンにB, C, Sなどの半金属や非金属イオンを注入することにより、可視光領域に吸収を示すことが期待されている。そこで、酸素欠陥型TiO2-X(X=B,C,S)に対するPBC計算を行い、それらのバンド構造を検討した。特に、BおよびCの注入により、価電子帯の上部に新たに準位が生じ、結果としてバンドギャップが小さくなることが示された。研究テーマ(2)では、クラスターモデルを用いて、水、メタノール、そしてギ酸の分解反応を理論的に検討した。熱反応(基底状態)に加えて、光反応のモデルとして、イオン化したクラスターの反応性を検討した。その結果、熱反応に比べ光反応では容易に反応が進行することが確かめられた。

固体及びクラスター表面反応のダイナミクスに関する理論的研究

2005

Research Results Outline:本特定課題研究では、分子軌道(MO)法や密度汎関数理論(DFT)などの第一原理手法を用いて、固体及びクラスター表面の触媒作用や機能発現の電子的機構を明本特定課題研究では、分子軌道(MO)法や密度汎関数理論(DFT)などの第一原理手法を用いて、固体及びクラスター表面の触媒作用や機能発現の電子的機構を明らかにすることを目指した。さらに、第一原理計算に基づいた力場を利用して分子動力学シミュレーションを...本特定課題研究では、分子軌道(MO)法や密度汎関数理論(DFT)などの第一原理手法を用いて、固体及びクラスター表面の触媒作用や機能発現の電子的機構を明らかにすることを目指した。さらに、第一原理計算に基づいた力場を利用して分子動力学シミュレーションを行うAIMD法により、表面反応のダイナミクスに関しても定量的な解析を目指した。具体的には、 (1)歪みシリコン表面の機能発現機構、および(2)星間分子衝突反応のダイナミクスとエネルギー移動、を当初の検討課題としていた。研究テーマ(1)では、ガウス基底を用いた周期境界条件(PBC)計算によって歪みシリコン表面の幾何構造及び電子状態を解明し、機能発現機構を理論的に検討した。特に、これらの理論的解析において、我々が独自に開発したエネルギー密度解析(EDA)をPBC計算と組み合わせること(PBC-EDA)の有効性が確かめられた。PBC-EDAの開発は、本プロジェクトと平行して行われ、まず種々のMgO表面(100)および(n10) (n=1-6)に対して応用された。そこでは、キンクやステップといった表面の各サイトの安定性や反応性を定量的に評価することに成功した。歪みシリコン表面に対しても、PBC-EDAにより歪みの影響を定量化することができた。研究テーマ(2)では、シアノラジカルとさまざまな不飽和炭化水素の衝突反応についてAIMDシミュレーションを実行し、そのダイナミクスとエネルギー移動を検討した。ここでは、上記のEDAをAIMDと組み合わせることにより、局所エネルギー変化の自己相関関数を求めることができ、さらにそれを短時間フーリエ変換(STFT)することにより化学反応におけるモード選択的なエネルギー分配のメカニズムを明らかすることができた。

実用的分子デバイスの設計および制御に向けた量子化学計算手法の開発

2006Collaborator:山内 佑介, 星野 稔

Research Results Outline:本研究の最終目標は、理論的手法に基づいた実用的分子デバイスの設計と制御である。そのために、ナノリンク分子の接合安定性と量子輸送現象を取り扱うための高精本研究の最終目標は、理論的手法に基づいた実用的分子デバイスの設計と制御である。そのために、ナノリンク分子の接合安定性と量子輸送現象を取り扱うための高精度な理論的手法の開発を目的とした。具体的には、電子および原子核の取り扱いに対する3種類のアプローチ...本研究の最終目標は、理論的手法に基づいた実用的分子デバイスの設計と制御である。そのために、ナノリンク分子の接合安定性と量子輸送現象を取り扱うための高精度な理論的手法の開発を目的とした。具体的には、電子および原子核の取り扱いに対する3種類のアプローチと電流に対する2種類のアプローチの融合を目指した。前者は主に量子化学理論を基盤としており、次のようなものである。第1が、Born-Oppenheimer(BO)近似により原子核の運動は分離して電子状態のみを扱う通常の分子軌道(MO)法や密度汎関数理論(DFT)などの量子化学計算である。第2は、原子核の運動を取り込むために、分子動力学(MD)法と組み合わせた方法がAIMD法である。更に、原子核の運動も量子的に扱えるものとして申請者らによるNOMO法があり、これが第3の方法である。後者は物性物理理論を基盤としておりKeldyshの摂動論に基づく非平衡グリーン関数(NEGF)法とKosovの定常電流Schrödinger方程式(CCSE)を直接解く方法である。本年度は、第1のアプローチに関して、従来定常状態にしか適用できなかったNOMO法を時間依存形式に拡張し、原子核の量子効果を考慮したダイナミックス(量子ダイナミックス)手法の基礎を確立した。また、第2のアプローチについては、AIMDシミュレーションのボトルネックである電子状態計算の高速化手法(LI-MO,LS-MO)を開発し、従来法に比べ3~5倍の計算時間の短縮に成功した。その他、分子-電極間安定接合の検証するために、我々が先に提案したエネルギー密度解析(EDA)を周期境界条件(PBC)計算に拡張した。さらに、このPBC-EDAが、表面構造の違いによる安定性・反応性の差異を定量的に評価できることを数値的に確認することができた。

インシリコ・ケミストリーの確立:分割統治法に基づいた大規模量子化学手法の開発

2009Collaborator:今村 穣, 渥美 照夫, 小林 正人, 佐藤 健

Research Results Outline:本研究の最終目標は、インシリコ・ケミストリーの確立である。まず、それに必要な高精度な大規模計算手法を開発するため,本研究では,理論の構築,プログラムの本研究の最終目標は、インシリコ・ケミストリーの確立である。まず、それに必要な高精度な大規模計算手法を開発するため,本研究では,理論の構築,プログラムの開発,そして実践という3段階で研究を進めた。当研究室ではこれまでに,全系を部分系に分割して計算する...本研究の最終目標は、インシリコ・ケミストリーの確立である。まず、それに必要な高精度な大規模計算手法を開発するため,本研究では,理論の構築,プログラムの開発,そして実践という3段階で研究を進めた。当研究室ではこれまでに,全系を部分系に分割して計算することにより計算コストを削減する手法,分割統治(DC)法に基づくHF,hybrid-DFT,MP2,CCSD法の理論および計算アルゴリズムを提案し,これら計算プログラムの開発を行ってきた。本研究では,現在標準的に用いられている計算方法のうち最も高精度なCCSD(T)にDC法を適用した(DC-CCSD(T))。また,エネルギー計算だけでなく動的分極率を計算するための計算手法にもDC法を拡張した。比較的低コストである密度汎関数理論(DFT)は,標準的な交換相関汎関数を用いる場合,分散力を記述できないという致命的な問題があった。本研究では局所応答近似に基づいて分散力を非経験的に算出するLRD法を考案し,弱い相互作用の高精度かつ効率的な計算を可能にした。また,量子化学計算に基づく分子シミュレーション手法を用いて,生体関連分子の立体構造の探索を行った。その際,当研究室で開発した分子構造の類似性の指標を用いて効率的に探索するMSMC法を用いた。

Foreign Countries Research Activity

Research Project Title: 電子状態理論におけるLinear -Scaling法の開発とその応用

2002/10-2003/10

Affiliation: ライス大学(アメリカ)

Lecture Course

Course TitleSchoolYearTerm
Science and Engineering Laboratory 1A IISchool of Fundamental Science and Engineering2018spring semester
Science and Engineering Laboratory 1A IISchool of Creative Science and Engineering2018spring semester
Science and Engineering Laboratory 1A IISchool of Advanced Science and Engineering2018spring semester
Science and Engineering Laboratory 1B IVSchool of Fundamental Science and Engineering2018fall semester
Science and Engineering Laboratory 1B IVSchool of Creative Science and Engineering2018fall semester
Science and Engineering Laboratory 1B IVSchool of Advanced Science and Engineering2018fall semester
Chemistry B1 Butsuri, Oubutsu (2)School of Advanced Science and Engineering2018spring semester
Basic Experiments in Science and Engineering 2B DenseiSchool of Advanced Science and Engineering2018spring semester
Physical Chemistry ASchool of Advanced Science and Engineering2018spring semester
Physical Chemistry A [S Grade]School of Advanced Science and Engineering2018spring semester
Physical Chemistry: ExerciseSchool of Advanced Science and Engineering2018fall semester
Physical Chemistry: Exercise [S Grade]School of Advanced Science and Engineering2018fall semester
Physical Chemistry : ExperimentSchool of Advanced Science and Engineering2018fall semester
Physical Chemistry : Experiment [S Grade]School of Advanced Science and Engineering2018fall semester
Graduation ThesisSchool of Advanced Science and Engineering2018full year
Graduation Thesis [S Grade]School of Advanced Science and Engineering2018full year
Quantum ChemistrySchool of Advanced Science and Engineering2018spring semester
Physical Chemistry LaboratorySchool of Advanced Science and Engineering2018fall semester
Physical Chemistry Laboratory [S Grade]School of Advanced Science and Engineering2018fall semester
Graduation Thesis ASchool of Advanced Science and Engineering2018fall semester
Graduation Thesis BSchool of Advanced Science and Engineering2018spring semester
Cluster-Seminar on Computational SciencesGraduate School of Advanced Science and Engineering2018spring semester
Master's Thesis (Department of Chemistry and Biochemistry)Graduate School of Advanced Science and Engineering2018full year
Research on Electronic State TheoryGraduate School of Advanced Science and Engineering2018full year
Research on Electronic State TheoryGraduate School of Advanced Science and Engineering2018full year
Advanced Electronic State TheoryGraduate School of Advanced Science and Engineering2018fall semester
Advanced Electronic State TheoryGraduate School of Advanced Science and Engineering2018fall semester
Advanced Electronic State TheoryGraduate School of Advanced Science and Engineering2018fall semester
Seminar on Electronic State Theory AGraduate School of Advanced Science and Engineering2018spring semester
Seminar on Electronic State Theory AGraduate School of Advanced Science and Engineering2018spring semester
Seminar on Electronic State Theory BGraduate School of Advanced Science and Engineering2018fall semester
Seminar on Electronic State Theory BGraduate School of Advanced Science and Engineering2018fall semester
Seminar on Electronic State Theory CGraduate School of Advanced Science and Engineering2018spring semester
Seminar on Electronic State Theory CGraduate School of Advanced Science and Engineering2018spring semester
Seminar on Electronic State Theory DGraduate School of Advanced Science and Engineering2018fall semester
Seminar on Electronic State Theory DGraduate School of Advanced Science and Engineering2018fall semester
Experiments in Chemistry and BiochemistryGraduate School of Advanced Science and Engineering2018full year
Special Laboratory on Chemistry and BiochemistryGraduate School of Advanced Science and Engineering2018full year
Master's Thesis (Department of Chemistry and Biochemistry)Graduate School of Advanced Science and Engineering2018full year
Research on Electronic State TheoryGraduate School of Advanced Science and Engineering2018full year
Special Seminar on Chemistry and Biochemistry AGraduate School of Advanced Science and Engineering2018spring semester
Special Seminar on Chemistry and Biochemistry BGraduate School of Advanced Science and Engineering2018fall semester
Special Seminar Abroad on Chemistry and BiochemistryGraduate School of Advanced Science and Engineering2018full year