THEORETICAL STUDY ON QUANTUM COUPLINGS BETWEEN CHARGE TRANSFER REACTION AND MEDIUM MODES

电荷转移反应与介质模式量子耦合的理论研究

• 批准号: 08640660
• 负责人: NAGAOKA Mistake
• 金额: $ 1.22万
• 依托单位: INSTITUTE FOR FUNDAMENTAL CHEMISTRY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 无数据
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640660/
• 关键词: Chemical Reaction MD Method; Stochastic Differential Equation; Solvent Effects; Generalized Langevin Equation; Classical-Quantum Coupled System; Nonequilibrium Distribution; Nonequilibrium Stationary State; Relaxation Process; 超溶質分子; 媒質性溶媒分子; 分子

In this Scientific Research Program (C), notifying arbitrary nonlinearity of the solutesolvent interaction in the hamiltonian for chemical reacting systems in condensed phase, the final research purposes were to formulate the reaction rate for the charge transfer reactions and to compare the numerical results with the experimental ones. In the term of project, in order to estimate the vibrational nonadiabaticity in the classical-quantum coupled systems, we proposed a new quantization method based on an equation of motion and have executed numerical treatment for the concentration and dissipative transfer of the reactive energy due to nonequilibrium induced by the vibrational nonadiabaticity in the present systems.1. A dividing surface is newly proposed in a many-body phase space, over which the system trajectories do not recross if the saddle crossing motions are regarded as quasiperiodic. The recrossing dynamics of a four degrees-of-freedom Hamiltonian, a model of proton transfer reac … More tion of malonaldehyde, is investigated. It is shown that the apparent barrier recrossing motions observed over a naive dividing surface in the configurational space are 'rotated away' by a nonlinear canonical transformation, to noreturn single crossing motions over the new dividing surface defined in the phase space.2. A stochastic Path-integral (SPI) technique is explored. It is shown that this technique enables the direct computation of the transition amplitude with a finite space-time range, by generating a set of classical paths subject to simultaneous stochastic differential equations.The numerical values of the Boltzmann matrix elements for a harmonic potential are in good agreement with the analytical ones. Within the quantum TS theory, the flux-flux autocorrelation function is also evaluated at 630K for the H+H_2 exchange reaction and is found to give a satisfactory agreement with the previous studies. To appraise the influence of the dimensionality, both 1-dimensional Eckart potential and a full 3D LSTH potential calculations have been perfomed. The calculated values of the Boltzmann matrix elements for the collinear and the full 3D cases are found to deviate slightly each other in the lower temperature range. The 3D thermal rate constant becomes in very good agreement with the previous one. Less

在这个科学研究计划(C)中，对于凝聚相化学反应体系，在哈密顿量中通知任意非线性的溶媒相互作用，最终的研究目的是描述电荷转移反应的反应速率，并将数值结果与实验结果进行比较。在项目方面，为了估算经典-量子耦合系统中的振动非绝热性，我们提出了一种新的基于运动方程的量子化方法，并对现有系统中由于振动非绝热性引起的非平衡反应能的集中和耗散转移进行了数值处理。在多体相空间中新提出了一种分割面，当鞍点交叉运动为准周期运动时，分割面上的系统轨迹不再交叉。质子转移反应…模型--四自由度哈密顿量的穿越动力学更多的丙二醛，被考察。结果表明，通过非线性正则变换，在位形空间中的初始分割面上观察到的表观势垒穿越运动被“旋转离开”，而不再返回在相空间中定义的新分割面上的单一交叉运动。探索了一种随机路径积分(SPI)技术。结果表明，该方法可以直接计算有限时空范围内的跃迁振幅，方法是生成一组满足同时随机微分方程组的经典路径，求出的简谐势的Boltzmann矩阵元的数值与解析解符合得很好。在量子TS理论中，还计算了H+H_2交换反应在630K下的通量-通量自相关函数，结果与前人的研究结果令人满意地吻合。为了评价维度的影响，我们进行了一维ECKART势和全三维LSTH势的计算。在较低的温度范围内，共线情况和全三维情况下的Boltzmann矩阵元的计算值略有偏差。计算得到的三维热速率常数与以前的结果吻合很好。较少

项目成果

Masataka Nagaoka: "Transition State Optimization on Free Energy Surface:Toward Solution Chemical Reaction Ergodography" International Journal of Quantum Chemistry. (印刷中). (1998)

Masataka Nagaoka：“自由能表面的过渡态优化：走向溶液化学反应 Ergodography”国际量子化学杂志（1998 年出版）。

Masataka Nagaoka: Potential Energy Function for Intramolecular Proton Trasfer Reaction of Glycine in Aqueous Solution. Journal of Physical Chemistry. 1998 (102)

Masataka Nagaoka：水溶液中甘氨酸分子内质子转移反应的势能函数。

Masataka Nagaoka: "A dividing Surface free from α Barrier Recrossing Motion in Many-Body Systems" Chemical Physics Letters. 265. 91-98 (1997)

Masataka Nagaoka：“多体系统中不受 α 势垒重新交叉运动影响的分割表面”《化学物理快报》265. 91-98 (1997)。

Mistake Nagaoka: "Chemical Reactions in Condensed Phase and Stochastic Numerical Analyzes- - -Langevin Equation in Complex Time Stochastic Quantization- - -" Surikaiseki-Kenkyusho Kokyuroku. 1032. (1998)

错误 Nagaoka：“凝聚相中的化学反应和随机数值分析 - - -复杂时间随机量化中的朗之万方程 - - -” Surikaiseki-Kenkyusho Kokyuroku。

Mistake Nagaoka, Katsuhiro Suenobu and Tokio Yamabe: "On the Hydropnium Ion Catalyzed Mechanizum in Vinyl Alcohol-Acetaldehyde Isomerization : Ab inition Molecular Orbital Theory and Monte Carlo Simulation" Journal of American Chemical Society. 119. 8023-

Mistake Nagaoka、Katsuhiro Suenobu 和 Tokio Yamabe：“On the Hydropnium Ion Catalyzed Mechanizum in VinylAlcohol-Acetogenic Isomerization：A inition 分子轨道理论和蒙特卡洛模拟”美国化学会杂志。