2002 Fiscal Year Annual Research Report

リアル系のシミュレーションとダイナミクス

Research Project

Project/Area Number	14002004
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分子軌道法 / 多参照摂動論 / 相対論効果 / 密度汎関数法 / UTChem
Research Abstract	本研究の日的は「次世代分子理論」を開発するとともに、わが国で初めての本格的な分子理論計算のプログラム・パッケージ「UTChem」を開発し、リアル系のシミュレーションとダイナミクスに応用することにある。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数百から千原子系を扱える分子理論の構築とその実用化をめざしている。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)などの開発を行った。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 (SPS) SCF法、および、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新しい電子相関法であるLocal MP2法の開発した。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.非相対論の場合に提案されているHead-GordonとPopleによるtransfer relationを採用し,共通に計算できる積分を保持させることで高速積分計算を実現した。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。プログラム開発のUTChemプロジェクトについては今年度末までにプログラム・パッケージの基本設計を終えた。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、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てきた。広く一般の研究者に提供するため公開用プログラムの整備、マニュアルの作成、入出力インターフェイス/データの可視化プログラムの作成など、公開に向けて準備を行っている。以上のように当初の計画通り、研究は順調に進捗している。

Research Products
(26 results)

All Other

All Publications (26 results)

[Publications] Takao Tsunada, Mineaki 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, Yurii V.Gelettii, G.L.Hill, Kimihiko Hirao: "Can Ebselen Derivatives Catalyze the Isomerization of Peroxyritrite 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.Phycs.. (in press).
[Publications] Dmitri G.Fedrov, Takahito Nakajima, Kimihiko Hirao: "An ab initio study of excited states of U and UF"J.Chem.Phys.. 118. 4970-4975 (2003)
[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 ribrational state of H_2CO"J.Chem.Phycs.. 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, Takahite 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] M.Kamiya, T.Tsunede, K.hirao: "A density functional study of van der Waals interactions"J.Chem.Phys.. 117. 6010-6015 (2002)
[Publications] W.Iie, 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.knogh, 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.Pauloric, 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.Hida, 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.Kawashima, M.Dupuis, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model Extended to the Monte Carlo method : Application to the Blue Shift of the H_2CO^1(x^*←n) Excitation"J.Chem.Phys.. 117. 248-257 (2002)
[Publications] T.Tsuchiya, T.Nakajima, K.hirao, L.Seijo: "A third-order Douglas-Kroll 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.RO.Widimark, K.Hirao: "Theoretical study of the unusual potential energy curve of the A^1 Σ^+ 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 Referance Functions"J.Comp.Chem.. 23. 1166-1175 (2002)
[Publications] Y.Nakano, 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

リアル系のシミュレーションとダイナミクス

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 Tsunada, Mineaki 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, Yurii V.Gelettii, G.L.Hill, Kimihiko Hirao: "Can Ebselen Derivatives Catalyze the Isomerization of Peroxyritrite 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.Phycs.. (in press).

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

[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 ribrational state of H_2CO"J.Chem.Phycs.. 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, Takahite 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] M.Kamiya, T.Tsunede, K.hirao: "A density functional study of van der Waals interactions"J.Chem.Phys.. 117. 6010-6015 (2002)

[Publications] W.Iie, 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.knogh, 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.Pauloric, 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.Hida, 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.Kawashima, M.Dupuis, K.Hirao: "The QM/MM-pol-vib/CAV Solvation Model Extended to the Monte Carlo method : Application to the Blue Shift of the H_2CO^1(x^*←n) Excitation"J.Chem.Phys.. 117. 248-257 (2002)

[Publications] T.Tsuchiya, T.Nakajima, K.hirao, L.Seijo: "A third-order Douglas-Kroll 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.RO.Widimark, K.Hirao: "Theoretical study of the unusual potential energy curve of the A^1 Σ^+ 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 Referance Functions"J.Comp.Chem.. 23. 1166-1175 (2002)

[Publications] Y.Nakano, 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)