2002 Fiscal Year Annual Research Report

次世代分子理論の開発

Research Project

Project/Area Number	13853007
Research Institution	The University of Tokyo
Principal Investigator	平尾公彦東京大学, 大学院・工学系研究科, 教授 (70093169)
Co-Investigator(Kenkyū-buntansha)	常田貴夫東京大学, 大学院・工学系研究科, 助手 (20312994) 中嶋隆人東京大学, 大学院・工学系研究科, 助手 (10312993) 中野晴之東京大学, 大学院・工学系研究科, 助教授 (90251363)
Keywords	分子理論 / ab initio理論 / 多参照摂動論 / 相対論 / 密度汎関数法 / UTChem
Research Abstract	本研究の目的は新しい分子理論の開発やアルゴリズム、ソフトウエアの開発をもとに、モデル系ではなくリアル系を対象とした「次世代分子理論」を開発することにある。年度の当初に特別推進研究「リアル系のシミュレーションとダイナミクス」が採択されたために、本基盤研究Sは辞退した。研究は特別推進研究に引き継がれ、大きな成果をあげている。そのいくつかを以下に記す。大規模分子にも適用できるab initio分子軌道理論として、多配置摂動論(MRMP, MC-QDPT)などの開発を行い、分子の励起スペクトル、化学反応に適用してきた。これまで開発してきた理論的手法を土台にした適用可能な系の拡張、アルゴリズム、プログラムの整備、および、これまでとは異なった視点から新たに大規模系にアプローチする手法の探索を目的として研究を行った。具体的には、1.新しいMCSCF法であるstring product space SCF法、およぴ、それを基礎とした摂動論の開発、2.非直交Kohn-Sham DFT法、3.新しい多参照Brillouin-Wigner摂動論の開発、4.局在化軌道を利用したLocal MP2法の開発である。相対論的方程式に基づいた相対論的分子理論の開発にも力を注いだ。Dirac方程式は4成分の波動関数を持つので、実際に分子系に適用する場合には多大な計算量が必要となる。4成分相対論的Hamilton演算子に基づく分子理論とその近似となる相対論的近似Hamilton演算子に基づく分子理論を展開し、相対論的分子積分アルゴリズムの更なる改良を行った。われわれの相対論的分子積分のアルゴリズムは世界最速である。また多電子系の相対論的Hamilton演算子に対する相対論的方程式であるDHF方程式及びDKS方程式が1電子方程式であることに着目し、これらの一体ポテンシャルに対しDK変換を施す方法を開発した。さらに4成分Dirac-Hartree-Fock法に電子相関効果を取り込むために、原子積分から分子積分への積分変換の新しいアルゴリズムを開発した。DFT法ではこれまで扱うことができなかったvan der Waals相互作用を取り入れる新しい理論を開発した。また、領域的自己相互作用補正(RSIC)法による化学反応障壁エネルギー過小評価の改善した。UTChemプログラム開発においては基本設計を終え、量子化学の計算において必須であるHartree-Fock法、密度汎関数法、および、CI法、Moller-Plesset摂動法、coupled-cluster法などの電子相関法に加えて分子構造の探査に必要な構造最適化法、相対論的分子軌道法などのプログラムを整備した。

Research Products

(26 results)

All Other

All Publications (26 results)

[Publications] Takao Tsuneda, Muneaki Kamiya, Kimihiko Hirao: "Regional self-interaction correction of density functional theory"J. Comput. Chem. (in press).
[Publications] H.Yui, T.Nakajima, K.Hirao, T.Sawada: "Enhancement of the stimulated Raman scattering derived from intermolecular interactions between aromatic moieties"J. Phys. Chem. A. 107. 968-973 (2003)
[Publications] D.G.Musaev, K.Hirao: "The Differences and Similarities in the Reactivities of Peroxynitrite Anion and Peroxynitrous Acid with Ebselen. A Theoretical Study"J. Phys. Chem.. (in press).
[Publications] D.G.Musaev, Yuri V.Gelettii, G.L.Hill, Kimihiko Hirao: "Can Ebselen Derivatives Catalyze the Isomerization of Peroxynitrite to Nitrate?"J. Amer. Chem. Soc.. (in press).
[Publications] Henryk A.Witek, Haruyuki Nakano, Kimihiko Hirao: "Multireference pertubation theory with optimized partitioning. I.Theoretical and computational aspects"J. Chem. Phys.. (in press).
[Publications] Dmitri G.Fedorov, Takahito Nakajima, Kimihiko Hirao: "An ab initio study of excited states of U and UF"J. Chem. Phys.. 118. 4970-4975 (2003)
[Publications] M.Kamiya, T.Tsuneda, K.Hirao: "A density functional study of van der Waals interactions"J. Chem. Phys.. 117. 6010-6015 (2002)
[Publications] W.lie, D.G.Fedrov, K.Hirao: "Theoretical study of the reaction XY_4=XY_3+Y, where X=C Si, Ge, Sn, PB and Y=CH_3, C_2H_5"J. Phys. Chem.. A106. 7057-7061 (2002)
[Publications] R.Lindh, J.W.Krogh, M.Schutz, K.Hirao: "Semi-direct parallel SCF : the load balancing in the I/O intensive SCF iterations"Theor. Chem. Acc.. (in press).
[Publications] J.Paulovic, T.Nakajima, K.Hirao, L.Seijo: "Third-order Douglas-Knoll ab initio model potential for actinides"J. Chem. Phys.. 117. 3597-3604 (2002)
[Publications] M.Dupuis, Y.Kawashima, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model With Polarizable MM for Excited States : II Application to the Blue Shift in H_2CO^1(π^*←n) Excitation"J. Chem. Phys.. 117. 1255-1268 (2002)
[Publications] M.Dupuis, M.Aida, Y.Kawashima, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model With Polarizable MM for Excited States : I, Energy and Gradients Formulation and Implementation"J. Chem. Phys.. 117. 1242-1255 (2002)
[Publications] Y.Yokoyama, J.P.Finley, H.Nakano, K.Hirao: "Maximum radius of convergence perturbation theory : test calculations on Be, Ne, H_2 and HF"Theor. Chem. Acc.. (in press).
[Publications] K.Yagi, C.Oyanagi, T.Taketsugu, Kimihiko Hirao: "Ab initio potential energy surface for vibrational state of H_2CO"J. Chem. Phys.. 118. 1653-1660 (2003)
[Publications] Shinji Ikeda, Takahito Nakajima, Kimihiko Hirao: "A Theoretical Study of Transition Metal Hydroxides : CuOH, AgOH, and AuOH"Mol. Phys (Yoshimine Memorial Issue). 101. 105-110 (2003)
[Publications] Y.Ishikawa, T.Nakajima, T.Yanai, K.Hirao: "Ab initio direct molecular dynamics study of the fragmentation of F(H_2O)complex generated by photodetachement of (H_2O) anion complex"Chem. Phys. Lett.. 363. 458-464 (2002)
[Publications] Minori Abe, Takahito Nakajima, Kimihiko Hirao: "A theoretical study of the low-lying states of the AuSi molecule : An assignment of the excited A and D states"J. Chem. Phys.. 117. 7960-7967 (2002)
[Publications] D.Ajitha, D.G.Fedorov, J.P.Finley, K.Hirao: "Photodissociation of alkyl and aryl iodides and effect of fluorination : Analysis of proposed mechanisms and vertical excitations by spin-orbit ab initio study"J. Chem. Phys.. 117. 7068-7076 (2002)
[Publications] Y.Kawashima, M.Dupuis, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model Extended to the Maite Carlo Method : Application to the Blue Shift of the H_2CO^1(π^*←n) Excitation"J. Chem. Phys.. 117. 248-257 (2002)
[Publications] T.Tsuchiya, T.Nakajima, K.hirao, L.seijo: "A third-order Douglas-Knoll ab initio model potential for lanthanides"Chem. Phys. Lett.. 361. 334-340 (2002)
[Publications] T.Yanai, T.Nakajima, Y.Ishikawa, K.Hirao: "Highly efficient algorithm for electron repulsion integrals over relativistic four-component Gaussian-type spinors"J. Chem. Phys.. 116. 10122-10128 (2002)
[Publications] H.A.Witek, D.G.Fedrov, A.Viel, P-O.Widmark, K.Hirao: "Theoretical study of the unusual potential energy curve of the A ^1S^+ state of AgH"J. Chem. Phys.. 116. 8396-8406 (2002)
[Publications] T.Nakajima, Kimihiko Hirao: "Accurate relativistic Gaussian basis sets determined by the third-order Douglas-Kroll approximation with a finite-nucleus model"J. Chem. Phys.. 116. 8270-8275 (2002)
[Publications] K.Yagi, T.Taketsugu, K.Hirao: "A new analytic form of ab initio potential energy function : An application to H_2O"J. Chem. Phys.. 116. 3963-3966 (2002)
[Publications] H.Nakano, R.Uchiyama, K.Hirao: "Quasi-degenerate Perturbation Theory with General Multiconfiguration Self-Consistent Field Reference Functions"J. Comp. Chem.. 23. 1166-1175 (2002)
[Publications] Y.Nakao, Y.K.Choe, K.Hirao: "A CASCI-MRMP method based on Kohn-Sham orbitals"Mol. Phys. (Davidson : Special Issue). 100. 729-745 (2002)

2002 Fiscal Year Annual Research Report

次世代分子理論の開発

Principal Investigator

平尾 公彦 東京大学, 大学院・工学系研究科, 教授 (70093169)

Research Products

[Publications] Takao Tsuneda, Muneaki Kamiya, Kimihiko Hirao: "Regional self-interaction correction of density functional theory"J. Comput. Chem. (in press).

[Publications] H.Yui, T.Nakajima, K.Hirao, T.Sawada: "Enhancement of the stimulated Raman scattering derived from intermolecular interactions between aromatic moieties"J. Phys. Chem. A. 107. 968-973 (2003)

[Publications] D.G.Musaev, K.Hirao: "The Differences and Similarities in the Reactivities of Peroxynitrite Anion and Peroxynitrous Acid with Ebselen. A Theoretical Study"J. Phys. Chem.. (in press).

[Publications] D.G.Musaev, Yuri V.Gelettii, G.L.Hill, Kimihiko Hirao: "Can Ebselen Derivatives Catalyze the Isomerization of Peroxynitrite to Nitrate?"J. Amer. Chem. Soc.. (in press).

[Publications] Henryk A.Witek, Haruyuki Nakano, Kimihiko Hirao: "Multireference pertubation theory with optimized partitioning. I.Theoretical and computational aspects"J. Chem. Phys.. (in press).

[Publications] Dmitri G.Fedorov, Takahito Nakajima, Kimihiko Hirao: "An ab initio study of excited states of U and UF"J. Chem. Phys.. 118. 4970-4975 (2003)

[Publications] M.Kamiya, T.Tsuneda, K.Hirao: "A density functional study of van der Waals interactions"J. Chem. Phys.. 117. 6010-6015 (2002)

[Publications] W.lie, D.G.Fedrov, K.Hirao: "Theoretical study of the reaction XY_4=XY_3+Y, where X=C Si, Ge, Sn, PB and Y=CH_3, C_2H_5"J. Phys. Chem.. A106. 7057-7061 (2002)

[Publications] R.Lindh, J.W.Krogh, M.Schutz, K.Hirao: "Semi-direct parallel SCF : the load balancing in the I/O intensive SCF iterations"Theor. Chem. Acc.. (in press).

[Publications] J.Paulovic, T.Nakajima, K.Hirao, L.Seijo: "Third-order Douglas-Knoll ab initio model potential for actinides"J. Chem. Phys.. 117. 3597-3604 (2002)

[Publications] M.Dupuis, Y.Kawashima, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model With Polarizable MM for Excited States : II Application to the Blue Shift in H_2CO^1(π^*←n) Excitation"J. Chem. Phys.. 117. 1255-1268 (2002)

[Publications] M.Dupuis, M.Aida, Y.Kawashima, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model With Polarizable MM for Excited States : I, Energy and Gradients Formulation and Implementation"J. Chem. Phys.. 117. 1242-1255 (2002)

[Publications] Y.Yokoyama, J.P.Finley, H.Nakano, K.Hirao: "Maximum radius of convergence perturbation theory : test calculations on Be, Ne, H_2 and HF"Theor. Chem. Acc.. (in press).

[Publications] K.Yagi, C.Oyanagi, T.Taketsugu, Kimihiko Hirao: "Ab initio potential energy surface for vibrational state of H_2CO"J. Chem. Phys.. 118. 1653-1660 (2003)

[Publications] Shinji Ikeda, Takahito Nakajima, Kimihiko Hirao: "A Theoretical Study of Transition Metal Hydroxides : CuOH, AgOH, and AuOH"Mol. Phys (Yoshimine Memorial Issue). 101. 105-110 (2003)

[Publications] Y.Ishikawa, T.Nakajima, T.Yanai, K.Hirao: "Ab initio direct molecular dynamics study of the fragmentation of F(H_2O)complex generated by photodetachement of (H_2O) anion complex"Chem. Phys. Lett.. 363. 458-464 (2002)

[Publications] Minori Abe, Takahito Nakajima, Kimihiko Hirao: "A theoretical study of the low-lying states of the AuSi molecule : An assignment of the excited A and D states"J. Chem. Phys.. 117. 7960-7967 (2002)

[Publications] D.Ajitha, D.G.Fedorov, J.P.Finley, K.Hirao: "Photodissociation of alkyl and aryl iodides and effect of fluorination : Analysis of proposed mechanisms and vertical excitations by spin-orbit ab initio study"J. Chem. Phys.. 117. 7068-7076 (2002)

[Publications] Y.Kawashima, M.Dupuis, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model Extended to the Maite Carlo Method : Application to the Blue Shift of the H_2CO^1(π^*←n) Excitation"J. Chem. Phys.. 117. 248-257 (2002)

[Publications] T.Tsuchiya, T.Nakajima, K.hirao, L.seijo: "A third-order Douglas-Knoll ab initio model potential for lanthanides"Chem. Phys. Lett.. 361. 334-340 (2002)

[Publications] T.Yanai, T.Nakajima, Y.Ishikawa, K.Hirao: "Highly efficient algorithm for electron repulsion integrals over relativistic four-component Gaussian-type spinors"J. Chem. Phys.. 116. 10122-10128 (2002)

[Publications] H.A.Witek, D.G.Fedrov, A.Viel, P-O.Widmark, K.Hirao: "Theoretical study of the unusual potential energy curve of the A ^1S^+ state of AgH"J. Chem. Phys.. 116. 8396-8406 (2002)

[Publications] T.Nakajima, Kimihiko Hirao: "Accurate relativistic Gaussian basis sets determined by the third-order Douglas-Kroll approximation with a finite-nucleus model"J. Chem. Phys.. 116. 8270-8275 (2002)

[Publications] K.Yagi, T.Taketsugu, K.Hirao: "A new analytic form of ab initio potential energy function : An application to H_2O"J. Chem. Phys.. 116. 3963-3966 (2002)

[Publications] H.Nakano, R.Uchiyama, K.Hirao: "Quasi-degenerate Perturbation Theory with General Multiconfiguration Self-Consistent Field Reference Functions"J. Comp. Chem.. 23. 1166-1175 (2002)

[Publications] Y.Nakao, Y.K.Choe, K.Hirao: "A CASCI-MRMP method based on Kohn-Sham orbitals"Mol. Phys. (Davidson : Special Issue). 100. 729-745 (2002)

平尾公彦東京大学, 大学院・工学系研究科, 教授 (70093169)