Simple Flux-Side Formulation of State-Resolved Thermal Reaction Rates for Ring-Polymer Surface Hopping.
Simple Flux-Side Formulation of State-Resolved Thermal Reaction Rates for Ring-Polymer Surface Hopping.
复制标题
DOI：
10.1021/acs.jpca.9b00877
复制
发表时间：
2019-02
期刊：
影响因子：
--
通讯作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller
中科院分区：
文献类型：
--
作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller
采用最近开发的同构哈密顿框架，包括核量子效应的混合量子经典非绝热动力学，我们提出了一个通量侧制定的状态分辨的热反应速率的环聚合物表面跳跃（iso-RPSH）。一个有吸引力的方面的新方法是，多个状态分辨的非绝热热反应速率的计算，使只有一个自由能表面计算，而以前的非绝热通量面配方的表面跳跃涉及多个自由能表面计算。该方法被证明是强大的，直接实现，和数值结果表明，RPSH同构的哈密顿框架导致更好的分割面的独立性比替代RPSH方法，由于改进的保存路径积分统计。
Employing the recently developed isomorphic Hamiltonian framework for including nuclear quantum effects in mixed quantum-classical nonadiabatic dynamics, we present a flux-side formulation of state-resolved thermal reaction rates for ring-polymer surface hopping (iso-RPSH). An appealing aspect of the new approach is that calculation of multiple state-resolved nonadiabatic thermal reaction rates is enabled with only a single free-energy surface calculation, whereas previous nonadiabatic flux-side formulations for surface hopping involve multiple free-energy surface calculations. The method is shown to be robust and straightforwardly implemented, and numerical results reveal that RPSH in the isomorphic Hamiltonian framework leads to better dividing surface independence than alternative RPSH methods due to improved preservation of the path-integral statistics.