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开发一个强大的框架从头建模的溶剂对反应动力学的影响，从一个新的量子经典方法在我们的小组最近开发的。它有很好的定义广泛的适用性限制，是免费的固有缺陷，在标准的混合方法，如轨迹表面跳跃计划，平均场近似，或量子经典刘维尔方程。为此，我们计划调查的准确性和适用性的经典力学描述的反应坐标使用几个参考模型，并制定一个efficient数值实现我们的方法，基于从头算分子动力学描述的经典自由度。我们还计划直接从反应对的哈密顿量出发实现可逆孪生复合反应的非唯象模拟，并探讨相干性和退相对非绝热反应中分支比的作用。

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.