化学反応の動力学理論

1992 Fiscal Year Annual Research Report

• Project/Area Number: 04243105
• Research Institution: Okazaki National Research Institutes
• Principal Investigator: 中村 宏樹 岡崎国立共同研究機構, 分子科学研究所, 教授 (10010935)
• Co-Investigator(Kenkyū-buntansha): 山下 晃一 基礎化学研究所, 主任研究員 (40175659) ; 松沢 通生 電気通信大学, 教授 (10010943) ; 藤村 勇一 東北大学, 理学部, 助教授 (90004473) ; 立花 明知 京都大学, 工学部, 講師 (40135463) ; 高塚 和夫 名古屋大学大学院, 人間情報学研究科, 教授 (70154797)
• Keywords: 非断熱遷移 / 反応動力学 / 超励起状態 / 大振幅振動 / レーザー誘起動力学 / 波束動力学 / 高振動励起状態 / 超球座標法

Research Abstract

以下に述べる通り幅広い分野において多くの実績があげられた。
(1)非断熱遷移理論の開発(中村):有名なランダウ・ジーナ問題の厳密解析解及び有名な近似解析解を求めた。基本となる微分方程式のストークス定数の厳密解の導出。周期性非断熱トンネル現象の解析。
(2)原子移行反応動力学(中村):量子力学的厳密数値解(超球座標法)のJ≠0への拡張。WKB法に基づく多次元トンネル理論の構築。
(3)大きな反応系の理論(中村):分離曲面解析法によるクラスター内反応と古典カオスの解析。RRKM理論適用条件の明確化。
(4)超励起状態の研究(中村、崎本、高木):2電子励起状態の電子相関の解明。外場中のおける動力学の究明。解離性再結合過程の詳細解明。
(5)衝突誘起解離過程(崎本):連続状態の離散化による解離過程の取扱い。超球座標及びDVR法による共線系の解明。
(6)相空間上の大振幅振動(高塚):位相空間のダイナミカルバリアが形成するセパラトリックスに係る大振幅運動の理論の構築。
(7)プロトン移動、水素引抜き及び電子移動反応(立花):イオンー分子反応NH_3^++NH_3における標記反応の解析。機構の同定と定量的評価。
(8)強い非定常レーザー場中の波束動力学(藤村):光学遷移と反応動力学の相関を取入れた方法論の開発。
(9)2電子励起原子の動力学(松沢):多価イオン及び陽子(反陽子)によるHeの2電子励起、2電子励起状態の係る光イオン化及び2重イオン化過程の超球座標法による解明。
(10)共鳴散乱状態の解析(山下):複素DVR法に基づく解析法の開発と応用。
(11)波束動力学と高振動励起状態(山下):チェビシェフ多項式を用いた時間依存シュレーディンガー方程式の安定した数値解法の開発。

Research Products

• [Publications] M.Bear: "Variational Principles for Reactive Collisions based based on the Generalized Lagrange Multiplier Method" J.Chem.Phys.96. 6565-6575 (1992)
• [Publications] M.Kimura: "Coupled Channel Treatment of Transitions between Na(^2P_1/2,mj)and Na(^2P_3/2mj')in Collision with Na(^2S_1/2,mj'')" J.Chem.Phys.96. 7423-7432 (1992)
• [Publications] H.Nakamura: "Nonadiabatic Tunneling in One-Dimensional Finite Periodic Potential System" J.Chem.Phys.97. 256-264 (1992)
• [Publications] C.Zhu: "The Two-State Linear Curve Crossing Problems Revisited.I.Analysis of Stokes Phenomenon and Expressions for Scattering Matrices" J.Chem.Phys.97. 1892-1904 (1992)
• [Publications] C.Zhu: "Stokes Constants for a Certain Class of Second-Order Ordinary Differential Equations" J.Math.Phys.33. 2697-2717 (1992)
• [Publications] C.Zhu: "The Two-State Linear Curve Crossing Problems Revisited.II.Analytical Approximations for the Stokes Constant and Scattering Matrix:The Landau-Zener Case" J.Chem.Phys.97. 8497-8514 (1992)
• [Publications] C.Zhu: "The Two-State Linear Curve Crossing Problems Revisited.III.Analytical Approximations for the Stokes Constant and Scattering Matrix:Nonadiabatic Tunneling Case" J.Chem.Phys.98. (1993)
• [Publications] K.Someda: "Decoupling Surface Analysis of Classical Irregular Scattering and Clarification of Its Icide Structure" J.Chem.Phys.98. 1156-1169 (1993)
• [Publications] M.Iwai: "Electron Correlation in Doubly Excited States of the Hydrogen Molecule" Phys.Rev.A. (1993)
• [Publications] C.Zhu: "Numerical Method for the Two-State Linear Curve Crossing:Nonadiabatic Tunneling Case" Comp.Phys.Commun.74. 9-17 (1993)
• [Publications] K.Sakimoto: "Theory of Ion-Hydrogen Collisions in a Uniform Magnetic Field" J.Phys.B:At.Mol.Opt.Phys.25. 3641-3654 (1992)
• [Publications] K.Sakimoto: "Theory of Ion-hydrogen Collisions in a Uniform Magnetic Field II" J.Phys.B:At.Mol.Opt.Phys.25. 5399-5411 (1992)
• [Publications] K.Takatsuka: "Dynamics and Quantization of Hamiltonian Chaos:Density of States in Phase-Space Semiclassical Mechanics" Phys.Rev.A45. 4326-4339 (1992)
• [Publications] K.Takatsuka: "Extraction of Accurate Frequencies from the Fast-Fourier-Transform Spectra" J.Comp.Phys.374-380 (1992)
• [Publications] K.Takatsuka: "Concept of Phase-Space Large Amplitude Motion.A Classical Study" Chem.Phys.Lett.(1993)
• [Publications] A.Tachibana: "Atomic Orbital-Wise Characterization of the Vibronic Attractive Interaction in a Model of an Oxygen-Containing Organic Polymer" Can.J.Chem.70. 427-433 (1992)
• [Publications] A.Tachibana: "Finite-Size Dimensional Analysis of the Superconducting Vibronic Interaction" Int.J.Quant.Chem.41. 273-279 (1992)
• [Publications] A.Tachibana: "Reaction Ergodography for Silicon Nitridr Bond Formation by the Nitridation of Silicon Dioxide" J.Phys.Chem.96. 3029-3033 (1992)
• [Publications] A.Tachibana: "A Quantum Chemical Study of Interchain Hopping Model of Negatively Charged Solitons in Polyacetylene" Int.J.Quant.Chem.41. 461-474 (1992)
• [Publications] T.X.Lu: "Vibronic Dressed Electronic States and Nonadiabatic Effects in Polyacetylene" Int.J.Quant.Chem.42. 425-438 (1992)
• [Publications] T.X.Lu: "Molecular Dynamic Structure and Dimerization of Polyacetylene" Int.J.Quant.Chem.41. 475-488 (1992)
• [Publications] A.Tachibana: "Spontaneous Pair-Bond Scission Reaction between SiH_4 and F_2" Chem.Phys.Lett.199. 281-285 (1992)
• [Publications] A.Tachibana: "Dynamic Stability of Silacarbonyl Ylide" Int.J.Quant.Chem.42. 929-939 (1992)
• [Publications] A.Tachibana: "Effect of Ion Vibration for the Proton-Transfer Reaction of the Ammonia Cation.II.Classical Trajectory Calculation of an Orientational Effect" J.Chem.Phys.97. 4921-4928 (1992)
• [Publications] A.Tachibana: "External Field Effects for Chemical Reaction" Trends Phys.Chem.3. 7-15 (1992)
• [Publications] A.Tachibana: "SiH_3 Radical Mechanisms for Si-N Bond Formation" J.Am.Chem.Soc.114. 7504-7507 (1992)
• [Publications] A.Tachibana: "The Bond Nature and Reactivity of Silicon Compounds" Rev.Heteroatom Chem.6. 76-93 (1992)
• [Publications] A.Tachibana: "On the Redistribution of Electrons for Chemical Reaction Systems" Int.J.Quant.Chem.41. 527-555 (1992)
• [Publications] A.Tachibana: "Vibronic Attractive Interaction for Superconductivity in a Local Model of C_<60>" Chem.Phys.Left.(1992)
• [Publications] M.Sugawara: "Non-Markovian Effects of Intermolecular Vibrational Coherence on Femtosecond Time-resoved Coherent Anti-Stokes Raman Scattering from Molecules in Condensed Phases" Chem.Phys.Letts.189. 346-352 (1992)
• [Publications] Y.Nomura: "Vibronic Coherence between the Sequential Transitions in Two-photon Processed induced by Phase-incoherent Light Beams" Phys.Rev.A. 45. 4855-4863 (1992)
• [Publications] Y.Fujimura: "Mechenism of External Magnetic Field Dependent Fluorescence Decays of Gaseous Carbon Disulfide" Chem.Phys.162. 205-212 (1992)
• [Publications] T.Kato: "Effects of Intermolecular Vibronic Dephasing on Time-resolved Sum-frequency Generation from Molecules at an Interface" Chem.Phys.Letts.194. 380-385 (1992)
• [Publications] M.Hayashi: "Orgin of Subpicosecond Decay Components Revealed in Time-profiles of Coherent Anti-Stokes Raman Scattering from Neat Benzene" Chem.Phys.Letts.196. 44-50 (1992)
• [Publications] Y.Nomura: "Theoretical and Experimental Study on the Profile of Pump-probe Time-resolved Intensity Correlation Spectroscopy with Incoherent Light Beams" Chem.Phys.Letts.197. 405-412 (1992)
• [Publications] D.Ray: "Doubly Excited ^1F^0 States of Two-electrons--A Time-dependent Variation-perturbation Calculation" Phys.Lett.A. 169. 452-457 (1992)
• [Publications] K.Moribayashi: "Hyperspherical Approach to Double-electron Excitation of He by Fast-ion Impact. III Excitation to the (21,21') Manifold by Multiply-charged Ion Impact" Phys.Rev.A. 46. 1684-1687 (1992)
• [Publications] K.Moribayashi: "Hyperspherical Approach to Double-electron Excitation of He by Fast-ion Impact.IV Excitation to the (21,31') and (31,31') Manifolds by Multiply-charged Ion Impact" Phys.Rev.A.
• [Publications] J.Z.Tang: "General Computational Method for Two Electron Systems" Phys.Rev.A. 46. 2437-2444 (1992)
• [Publications] J.Z.Tang: "Dipole Density Function and Evaluation of the Osicillator Strength of He" Phys.Rev.A. 46. 3758-3761 (1992)
• [Publications] J.Z.Tang: "Evidence of an Excited Angular Correlation Mode in High-lying He^-" Phys.Rev.Lett.69. 1633-1635 (1992)
• [Publications] K.Yamashita: "Calculation on the Rate of the Ion-molecule Reaction C_2H_2^++H_2→C_2H_3+H" J.Chem.Phys.96. 5801-5807 (1992)
• [Publications] K.Yamashita: "New Ab Initio Potential Surfaces and Three-Dimensional Quantum Dyanmics for Transition State Spectroscopy in Ozone Photodissociation" Chem.Phys.Lett.191. 515-520 (1992)
• [Publications] E.Herbst: "Calculations of Interstellar Radiative Association Rates Including Tunneling,The Strange Case of C_2H_2^++H_2" J.Chem.Soc.Faraday Transactions. (1993)
• [Publications] S.Takada: "Advances in Molecular Vibrations and Collision Dynamics:Quantum Reactive Scattering" JAI, (1993)
• [Publications] S.Lee: "Molecules in Laser Fields" Marcel Dekker, (1993)
• [Publications] H.Takagi: "Theoretical Problems in the Dissociative Recombination of H_2^++e,Dissociative Recombination:Theory Experiment,and Applications" Plenum,
• [Publications] M.Hayashi: "Effects of Intermolecular Vibrational Dephasing on Time-Resolved Coherent Anti-Stokes Raman Scattering from Molecules in Liq1id" Springer-Verlag,
• [Publications] Y.Fujimura: "Dynamical Effects on U1 trashort Time-Resolved Nonlinear Coherent Scattering from Molecules in Condensesd Phases" Springer-Verlag, (1992)
• [Publications] M.Sugawara: "Vibrational Wave Packet Dynamics of Diatomic Molecules Under Intense U1tra-Short Laser Pulses" Springer-Verlag, (1992)