Ultrafast reaction dynamics in condensed phase: Solvent impact on pathways and mechanisms of elementary chemical processes

该项目的主要目标是从我们小组最近开发的一种新的量子经典方法开始，开发一个强大的框架，用于从头计算模拟溶剂对反应动力学的影响。它具有定义明确的广泛适用范围，并且没有标准混合方法所固有的缺陷，如弹道表面跳跃方案、平均场近似或经典量子Liouville方程。为此，我们计划使用几个参考模型来研究反应坐标的经典力学描述的准确性和适用性，并基于经典自由度的从头算分子动力学描述来开发我们方法的有效数值实现。我们还计划直接从反应对的哈密顿量出发实现可逆双酯复合反应的非唯象模拟，并探索相干和退相对支化比在非绝热反应中的作用。

The main goal of the project is to develop a powerful framework for ab initio modeling of solvent effects on reaction dynamics starting from a novel quantum-classical methodology recently developed in our group. It has well defined wide applicability limits, and is free from defects inherent in standard hybrid approaches like trajectory surface hopping schemes, mean-field approximations, or the quantum-classical Liouville equation. Towards this end we plan to investigate the accuracy and applicability of a classical mechanics description of reaction coordinates using several reference models, and to develop an effcient numerical implementation of our approach, based on an ab initio molecular dynamics description of classical degrees of freedom. We also plan to achieve non-phenomenologic modeling of reversible geminate recombination reactions starting directly from the Hamiltonian of reactive pair, and to explore the role of coherence and dephasing for the branching ratios in nonadiabatic reactions.