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

在本研究计划（C）中，提出了凝聚相化学反应体系哈密顿量中溶质-溶剂相互作用的任意非线性，最终研究目的是建立电荷转移反应的反应速率公式，并将数值计算结果与实验结果进行比较。在项目期间，为了估计经典-量子耦合系统中的振动非绝热性，我们提出了一种基于运动方程的量子化方法，并对本系统中由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.在多体相空间中提出了一个新的分界面，如果鞍形交叉运动被认为是准周期的，则系统的轨迹不会在该分界面上交叉。研究了质子转移反应模型--四自由度哈密顿量的再交叉动力学， ...更多信息 对丙二醛的降解进行了研究。结果表明，在位形空间中的一个初始分割面上观察到的表观势垒重交叉运动通过一个非线性正则变换被“旋转离开”，成为在相空间中定义的新分割面上的不返回单交叉运动.探索了随机路径积分（SPI）技术。结果表明，这种方法通过产生一组经典路径，直接计算有限时空范围内的跃迁振幅，得到了与解析解一致的调和势的Boltzmann矩阵元数值.在量子TS理论下，计算了630 K下H+H_2交换反应的通量-通量自相关函数，与前人的研究结果符合较好。为了评价维数的影响，我们对一维Eckart势和全三维LSTH势进行了计算。共线和全三维情况下的玻尔兹曼矩阵元的计算值被发现在较低的温度范围内彼此略有偏离。3D热速率常数变得与前一个非常好的协议。少

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