量子的化学原理の深化と実現

2006 Fiscal Year Annual Research Report

• Project/Area Number: 14GS0217
• Research Institution: Kyoto University
• Principal Investigator: 中辻 博 Kyoto University, 工学研究科, 名誉教授 (90026211)
• Co-Investigator(Kenkyū-buntansha): 加藤 重樹 京都大学, 理学研究科, 教授 (20113425) ; 榊 茂好 京都大学, 工学研究科, 教授 (20094013) ; 波田 雅彦 首都大学東京, 理工学研究科, 教授 (20228480) ; 江原 正博 京都大学, 工学研究科, 准教授 (80260149) ; 長谷川 淳也 京都大学, 工学研究科, 助教 (30322168)
• Keywords: 化学原理 / シュレーディンガー方程式の厳密解 / 理論精密分光学 / 生命量子論 / 巨大分子系 / 凝縮系 / 相対論的量子化学 / 遷移金属錯体

Research Abstract

シュレーディンガー方程式の解析解の一般的な解法:シュレーディンガー(SE)方程式とディラック・クーロン方程式の解析解の一般的な解法の研究をさらに推し進めた。Scaled-SEに基づくFree ICI法により、世界で最も正確な波動関数をヘリウムや水素分子イオンについて求めることに成功した。さらに積分操作を行うことなく解析解を求める方法、Local SE法(LSE法)を開発し、積分の困難を原理的に解消することに成功した。このLSE法により絶対エネルギーにおいて化学精度(kcal/mol)を超える正しい解を一般の原子・分子について計算できることを示した。
ファインなスペクトロスコピーと反応の量子ダイナミックス:精度が高く計算効率の上でも優れているdirect SAC-CI法を完成した。有機ELのIr錯体やアクリジン型バイオセンサーの光吸収・発光過程を定量的に明らかにした。最先端の実験と協力し、様々な内殻電子過程における励起ダイナミクスを解明した。
巨大分子系の電子状態理論の構築:巨大な分子性結晶・分子集合体・ポリマー等の電子状態を、構成分子の精密なSAC-CI波動関数と同程度の精度で構築する新たな理論-Giant SAC/SAC-CI理論を開発した。この方法を、幾つかの環状分子性結晶の基底状態と励起状態に応用し、光磁気センサーを設計することが可能であることを示した。
生体反応系の電子論とダイナミックスの解明:視覚で知られるレチナール蛋白質について研究し、レチナール色素のcolor-tuningメカニズムを定量的に明らかにした。蛍ルシフェリンの発光色制御メカニズムを研究し、蛋白質残基とそのクーロン場が発光色制御の要因であることを明らかにした。
凝縮系における反応の電子論とダイナミックス:溶液内光化学過程の研究において、自由エネルギー円錐交差点を求める方法を開発し、極性溶媒中での円錐交差の構造と溶媒効果について論じた。
表面-分子相互作用系と触媒反応の電子論:燃料電池で重要なPt表面上のアルコール酸化反応の反応メカニズムの研究を行った。Pd錯体によるアレンのシリルボリル化反応を理論的に研究し、幾つかの反応経路を検討した。

Research Products

• [Journal Article] Solving the Schrodinger and Dirac equations of hydrogen molecular ionaccurately by the free iterative complement interaction method (2008)
  • Author(s): A. Ishikawa, H. Nakashima, H. Nakarsuji
  • Journal Title: J. Chem. Phys. 128 Pages: 124103-1-12
• [Journal Article] Formulation and Implementation of Direct Algorithm for the Symmetry Adapted Cluster (SAC) and Symmetry Adapted Cluster-Configuration Interaction (SAC-CI) Method (2008)
  • Author(s): R. Fukuda and H. Nakatsuji
  • Journal Title: J. Chem. Phys. 128 Pages: 094105-1-14
• [Journal Article] Vibration-induced suppression of valence-Rydberg mixing in the 01s→ nssigma Rydberg series in N20 (2008)
  • Author(s): T. Tanaka, M. Hoshino, H. Kato, M. Ehara, N. Yamada, R. Fukuda, H. Nakatsuji, Y. Tamenori, J.R. Harries, G. Prumper, H. Tanaka, K. Ueda
  • Journal Title: Phys. Rev. A. 77 Pages: 012709-1-4
• [Journal Article] Mechanism of the Palladium-Catalyzed Redioselective Silaboration of Allene: Theoretical Study (2008)
  • Author(s): Y. Abe, K. Kuramoto, M. Ehara, H. Nakatsuji, M. Suginome, M. Murakami, Y. Ito
  • Journal Title: Organometallics (in press)
• [Journal Article] Excitation and Circular Dichroism Spectra of (-) - (3aS, 7aS)-2-chalcogena-trans-hydrindans (Ch=S, Se, Te): SAC and SAC-CI Calculations (2008)
  • Author(s): Y. Honda, A. Kurihara, M. Hada, H. Nakatsuji
  • Journal Title: J. Comp. Chem. 29 Pages: 612-621
• [Journal Article] An Ab initio study based on a finite nucleus model for isotope fractionation in the U (III)-U (IV) exchange reaction system (2008)
  • Author(s): M. Abe, T. Suzuki, Y. Fujii, and M. Hada
  • Journal Title: J. Chem. Phys. 128 Pages: 1443091-1-6
• [Journal Article] Effect of Tridentate Ligand on Structure, Electronic Structure, and Reactivity of Copper (I) Nitrite Complex: Role of Conserved Three-Histidines Ligand Environment of Type-2 Copper Site in Copper Containing Nitrite Reducatse (2008)
  • Author(s): M. Kujime, C. Izumi, M. Tomura, M. Hada, and H. Fujii.
  • Journal Title: J. Am. Chem. Soc. (in press)
• [Journal Article] Evaluation of Electron Population Term for <rse-3>4P, <rrs-3>3p, and <r0-3>2p: How do HOMO and LUMO Shrink or Spread Depending on Nuclear Charges? (2008)
  • Author(s): W. Nakanishi, S. Hayashi, K. Narahara, D. Yamaki, and M. Hada
  • Journal Title: Chemistry A European J. (in press)
• [Journal Article] Quantum-Chemical Calculations of Natural Circular Dichroism (2008)
  • Author(s): Y. Honda and M. Hada
  • Journal Title: Computing Letters (in press)
• [Journal Article] Solving the Schrodinger Equation of Atoms and Molecules without Analytical Integration Based on the Free Iterative-Complement-Interaction (ICI) Wave Function (2007)
  • Author(s): H. Nakatsuji, H. Nakashima, Y. Kurokawa, and A. Ishikawa
  • Journal Title: Phys. Rev. Lett. 99 Pages: 240402-1-4
• [Journal Article] Solving the Schrodinger Equation for Helium Atom and its Isoelectronic Ions with the Free Iterative Complement Interaction (ICI)Method (2007)
  • Author(s): H. Nakashima and H. Nakatsuji
  • Journal Title: J. Chem. Phys. 127 Pages: 224104-1-14
• [Journal Article] SAC (symmetry adapted cluster)/SAC-CI (configuration interaction) methodology extended to giant molecular systems: ring molecular crystals (2007)
  • Author(s): H. Nakatsuji, T. Miyahara, and R. Fukuda
  • Journal Title: J. Chem. Phys. 126 Pages: 084104-1-18
• [Journal Article] Coupling between substituents as a function of cage structure. Synthesis and valence ionized states of bridgehead disubstituted parent and hexafluorinated bicyclo [1.1.1] pentane derivatives, C5X6Y2 (2007)
  • Author(s): M. Ehara, S. Fukawa, H. Nakatsuji, D. David, E.Z. Pinkhassik, M. Apostol, J. Michl
  • Journal Title: Chemistry-An Asian Journal 2 Pages: 1007-1019
• [Journal Article] Red Light in Chemiluminescence and Yellow-green Light in Bioluminescence: Color-tuning Mechanism of Firefly, Photinus pyralis, studied by the SAC-CI method (2007)
  • Author(s): N. Nakatani, J. Hasegawa, H Nakatsuji
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 8756-8765
• [Journal Article] Excited States of GFP Chromophore and Active Site Studied by the SAC-CI method: Effect of Protein-environment and Mutations (2007)
  • Author(s): J. Hasegawa, K. Fujimoto, B. Swerts, T. Miyahara, and H. Nakatsuji
  • Journal Title: J. Comp. Chem. 28 Pages: 2443-2452
• [Journal Article] SAC-CI Theoretical Study on the Excited States of Lumiflavin: Structure, Excitation Spectrum, and Solvation Effect (2007)
  • Author(s): J. Hasegawa, S. Bureekaew, and H. Nakatsuji
  • Journal Title: J. Photochem. Photobiology A: Chemistry 189 Pages: 205-210
• [Journal Article] Investigation of the electronic spectra and excited state geometries of poly-para-phenylene vinylene and poly-para-phenylene by symmetry adapted cluster configuration interaction (SAC-CI) method (2007)
  • Author(s): B. Saha, M. Ehara, H. Nakatsuji
  • Journal Title: J. Phys. Chem. A 111 Pages: 5473-5481
• [Journal Article] Ground and Excited States of Singlet, Cation Doublet, and Anion Doublet States of o-Benzoquinone: A Theoretical Study (2007)
  • Author(s): Y. Honda, M. Hada, M. Ehara, H. Nakatsuji
  • Journal Title: J. Phys. Chem. A 111 Pages: 2634-2639
• [Journal Article] Vibrationally resolved central and terminal nitrogen K-shell photoelectron spectra of the dinitrogen oxide molecule (2007)
  • Author(s): M. Ehara, R. Tamaki, H. Nakatsuji, R. R. Lucchese, J. Soderstrom, T. Tanaka, M. Hoshino, M. Kitajima, H. Tanaka, A. De Fanis, K. Ueda
  • Journal Title: Chem. Phys. Lett. 438 Pages: 14-19
• [Journal Article] Active-space symmetry-adapted-cluster configuration-interaction for high accuracy calculations of potential energy surfaces of radicals (2007)
  • Author(s): Y. Ohtsuka, P. Piecuch, J. R. Gour, M. Ehara, H. Nakatsuji,
  • Journal Title: J. Chem. Phys. 126 Pages: 164111-1-28
• [Journal Article] Excited and ionized states of ozone studied by the MEG (multi-exponentially generated)/EX (excited)-MEG method (2007)
  • Author(s): Y. Ohtsuka, J. Hasegawa, and H. Nakatsuji
  • Journal Title: Chem. Phys. 322 Pages: 262-270
• [Journal Article] Symmetry and vibrationally resolved absorption spectra near the O K edge of N20: experiment and theory (2007)
  • Author(s): T. Tanaka, R. Feifel, H. Tanaka, M. Hoshino, M. Kitajima, L. Karlsson, K. Ueda, M. Ehara, R. Fukuda, R. Tamaki, H. Nakatsuji
  • Journal Title: Chem. Phys. Lett. 435 Pages: 182-187
• [Journal Article] Electronic excitations of fluoroethylene (2007)
  • Author(s): S. Arulmozhiraja, M. Ehara, H. Nakatsuji
  • Journal Title: J. Chem. Phys. 126 Pages: 044306-1-10
• [Journal Article] Theoretical Studies on the Color-Tuning Mechanism in Retinal Proteins (2007)
  • Author(s): K. Fujimoto, S. Hayashi, J. Hasegawa, and H. Nakatsuji
  • Journal Title: J. Chem. Theory Comput. 3 Pages: 605-618
• [Journal Article] Vibrationally resolved C and 01s photoelectron spectra of carbon dioxide (2007)
  • Author(s): T. Hatamoto, M. Matsumoto, X. -J. Liu, K, Ueda, M. Hoshino, K. Nakagawa, T. Tanaka, H. Tanaka, M. Ehara, R. Tamaki, H. Nakatsuji
  • Journal Title: J. Electron Spectrosc. Relat. Pheonom. 155 Pages: 54-57
• [Journal Article] Calculations of Frequency-Dependent Molecular Magnetizabilities with Quasi-Relativistic Time-Dependent Generalized Unrestricted Hartree-Fock Method (2007)
  • Author(s): T. Yoshizawa and M. Hada
  • Journal Title: J Comp Chem. 28 Pages: 740-747
• [Journal Article] How 77Se NMR Chemical Shifts Originate from Pre-α, α, β, and γ Effects: Interpretation Based on Molecular Orbital Theory (2007)
  • Author(s): W. Nakanishi, S. Hayashi, and M. Hada
  • Journal Title: Chemistry A European J. 13 Pages: 5282-5293
• [Journal Article] Applicability of the lowest-order two-electron Breit-Pauli relativistic correction in many-electron heavy and super-heavy elements (2007)
  • Author(s): J. Seino and M. Hada
  • Journal Title: Chem. Phys. Lett. 422 Pages: 134-139
• [Journal Article] An efficient implementation of three-dimensional reference interaction site model self-consistent-field method: Application to solvatochromic shift (2007)
  • Author(s): N. Minezawa, S. Kato
  • Journal Title: J. Phys. Chem, 126 Pages: 054511-1-15
• [Journal Article] Solvent effect on conical intersections in excited state 9H-adenine: Radiationless decay mechanism in polar solvent (2007)
  • Author(s): S. Yamazaki, S. Kato
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 2901-2909
• [Journal Article] Analytical RISM-MP2 free energy gradient method: Application to the Schlenk equilibrium of Grignard reagent (2007)
  • Author(s): T. Mori, S. Kato
  • Journal Title: Chem. Phys. Lett. 437 Pages: 159-163
• [Journal Article] Transition state determination of enzyme reaction on free energy surface (2007)
  • Author(s): M. Higashi, S. Hayashi, S. Kato
  • Journal Title: Chem. Phys. Lett. (in press)
• [Journal Article] Geometry optimization based on linear response free energy with quantum mechanical/molecular mechanical method: Applications to Menshutkin-type and Claisen rearrangement reactions in aqueous solution (2007)
  • Author(s): M. Higashi, S. Hayashi, S. Kato
  • Journal Title: J. Chem. Phys. (in press)
• [Journal Article] Binding Energies and Bonding Nature of MX(CO)(PH3)2(C60)(M=Rh or Ir; X=H or Cl). Theoretical Study (2007)
  • Author(s): A. Ikeda, Y. Kameno, Y. Nakao, H. Sato, S. Sakaki
  • Journal Title: J. Organomet. Chem. 692 Pages: 299-306
• [Journal Article] Inner-Shell Ionizations and Satellites Studied by the Open-Shell Reference (OR) Symmetry-Adapted Cluster (SAC)/SAC Configuration Interaction (CI) (2006)
  • Author(s): Y. Ohtsuka, H. Nakatsuji
  • Journal Title: J. Chem. Phys. 124 Pages: 054110-1-5
• [Journal Article] On the reversible O2 binding of the Fe-porphyrin complex (2006)
  • Author(s): H. Nakashima, J. Hasegawa, H. Nakatsuji
  • Journal Title: J. Comp. Chem. 27 Pages: 426-433
• [Journal Article] On the O2 binding of Fe-porphyrin, Fe-porphycene, and Fe-corrphycene complexes (2006)
  • Author(s): H. Nakashima, J. Hasegawa, H. Nakatsuji
  • Journal Title: J. Comp. Chem. 27 Pages: 1363-1372
• [Journal Article] On the color-tuning mechanism of Human-Blue visual pigment: SAC-CI and QM/MM study (2006)
  • Author(s): K. Fujimoto, J. Hasegawa, S. Hayashi, H. Nakatsuji
  • Journal Title: Chem. Phys. Lett. 432 Pages: 252-256
• [Journal Article] Electronic Circular Dichroism Spectrum of Uridine Studied by the SAC-CI method (2006)
  • Author(s): S. Bureekaew, J. Hasegawa, H. Nakatsuji
  • Journal Title: Chem. Phys. Lett. 425 Pages: 367-371
• [Journal Article] Quantum dynamics study on multichannel dissociation and isomerization reactions of formaldehyde (2006)
  • Author(s): T. Yonehara, S. Kato
  • Journal Title: J. Chem. Phys. 125 Pages: 084307-1-10
• [Journal Article] High resolution O 1s photoelectron satellite spectrum of H_2O (2006)
  • Author(s): R. Sankari, M. Ehaza, H. Nakatsuji, A. De Fanis, S. Aksela, S. L. Sorensen, M. N. Piancastelli, K. Ueda
  • Journal Title: Chem. Phys. Lett. 422 Pages: 51-57
• [Journal Article] C_4Cl: Bent or linear? (2006)
  • Author(s): S. Arulmozhiraja, M. Ehara, H. Nakatsuji
  • Journal Title: J. Chem. Phys. 125 Pages: 194314-1-7
• [Journal Article] SAC and SAC-CI Calculations of Excitation and Circular Dichroism Spectra of Straight-Chain and Cyclic Dichalcogens (2006)
  • Author(s): J. Seino, Y. Honda, M. Hada, H. Nakatsuji
  • Journal Title: J. Phys. Chem. A 110 Pages: 10053-10062
• [Journal Article] Vibrationally resolved C and O 1s photoelectron spectra of carbon monoxide (2006)
  • Author(s): M. Matsumoto, K. Ueda, E. Kukk, H. Yoshida, T. Tanaka, M. Kitajima, H. Tanaka, Y. Tamenori, K. Kuramoto, M. Ehaza, H. Nakatsuji
  • Journal Title: Chem. Phys. Lett. 417 Pages: 89-93
• [Journal Article] Electronic spectra and photodissociation of vinyl chloride-A SAC-CI study (2006)
  • Author(s): S. Arulmozhiraja, R. Fukuda, M. Ehara, H. Nakatsuji
  • Journal Title: J. Chem. Phys. 124 Pages: 034312-1-6
• [Journal Article] Symmetry-dependent vibrational excitation in N 1s photoionization of N_2: experiment and theory (2006)
  • Author(s): M. Ehara, H. Nakatsuji, M. Matsumoto, T. Hatamoto, X. -J. Liu, T. Lischke, G. Pruemper, T. Tanaka, C. Makochekanwa, M. Hoshino. H. Tanaka, J. R. Harries, Y. Tamenori, K. Ueda
  • Journal Title: J. Chem. Phys. 124 Pages: 124311-1-8
• [Journal Article] Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra (2006)
  • Author(s): B. Saha, M. Ehara, H. Nakatsuji
  • Journal Title: J. Chem. Phys. 125 Pages: 014316-1-14
• [Journal Article] Cls and O 1s photoelectron satellite spectra of CO with the symmetry-dependent vibrational excitations (2006)
  • Author(s): M. Ehara, K. Kuramoto, H. Nakatsuji, M. Hoshino, T. Tanaka, M. Kitajima, H. Tanaka, Y. Tamenori, A. De Fanis, K. Ueda
  • Journal Title: J. Chem. Phys. 125 Pages: 114304-1-10
• [Journal Article] Phosphorous-containing hybrid calixphyrins: Promising mixed-donor ligands for visible and efficient palladium catalysts (2006)
  • Author(s): Y. Matano, T. Miyajima, T. Nakabuchi, H. Imahori, N, Ochi, S. Sakaki
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 117600-11761
• [Journal Article] Silapropargyl/Silaallenyl and Silylene Acetylide Complexes of[Cp(CO)2W]+.Theoretical Study of Their Interesting Bonding Nature and Formation (2006)
  • Author(s): M. Ray, Y. Nakao, H. Sato, H. Sakaba, S. Sakaki
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 11927-11939
• [Journal Article] Deep Blue Mixed-Valenct PtIII-PtIII-PtII Complex[Pt3Br2(・-pz)6](pz=pyrazolate) Showing Valence-Detrapping Behavior in Solution (2006)
  • Author(s): K. Umakoshi, T. Kojima, Y. H. Kim, M. Ohnishi, Y. Nakao, S. Sakaki
  • Journal Title: Chem. Eur. J. 12 Pages: 6521-6527
• [Journal Article] Theoretical Study of Rhenium Dimer Complexes: Re-Re Bonding Nature and Electronic Structure (2006)
  • Author(s): K. Saito, Y. Nakao, H. Sato, S. Sakaki
  • Journal Title: J. Phys. Chem. A 110 Pages: 9710-9717
• [Journal Article] Ruthenium(II)-catalyzed hydrogenation of carbon dioxide to formic acid. Theoretical Study of Significant Acceleration by Water Molecule (2006)
  • Author(s): Y. Ohnishi, Y. Nakao, H. Sato, S. Sakaki
  • Journal Title: Organometallics 25 Pages: 3352-3363
• [Journal Article] Orientational Effect of Aryl Group on 77Se NMR Chemical Shifts: Experimental and Theoretical Investigations (2006)
  • Author(s): W. Nakanishi, S. Hayashi, D. Shimizu, M. Hada
  • Journal Title: Chemistry-A European Journal 12 Pages: 3829-3846