School of Advanced Materials, Peking University , Shenzhen Graduate School, Shenzhen, China 518055.
J Phys Chem A. 2013 Jul 18;117(28):5821-5. doi: 10.1021/jp404856p. Epub 2013 Jul 8.
Chemical reaction dynamics is always a central theme in chemistry research. In many important chemical processes, reaction dynamics is electronically nonadiabatic, i.e., dynamics involves coupled multiple electronic states. We demonstrate in this paper that a semiclassical (SC) treatment based on an initial value representation methodology and a classical mapping formalism for the electronic degrees of freedom is now able to provide a rigorous and practical solution to electronically nonadiabatic dynamics in complex molecular systems. The key component of this treatment is to incorporate a correlated importance sampling protocol in nonadiabatic SC calculations, which results in a speedup factor of 100 or more in comparison with that using the standard sampling approach. This is illustrated by application to a two-state model coupled with up to 10 nuclear bath modes for a benchmark nonadiabatic excitation energy transfer problem. This work provides great opportunities for the effectively theoretical investigations on reaction mechanisms in complex molecular systems, in which electronically nonadiabatic dynamics plays an importance role.
化学反应动力学一直是化学研究的核心主题。在许多重要的化学过程中，反应动力学是非绝热的，即动力学涉及耦合的多个电子态。本文证明，基于初始值表示方法和电子自由度的经典映射形式的半经典（SC）处理现在能够为复杂分子系统中的非绝热动力学提供严格而实用的解决方案。这种处理的关键组成部分是在非绝热 SC 计算中纳入相关重要性抽样协议，这导致与使用标准抽样方法相比，速度提高了 100 倍或更多。通过将其应用于与多达 10 个核浴模式耦合的两态模型来验证该基准非绝热激发能转移问题。这项工作为在复杂分子系统中有效地理论研究反应机制提供了机会，在这些系统中，非绝热动力学起着重要作用。
