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

凝聚相超快反应动力学：溶剂对基本化学过程的途径和机制的影响

• 批准号: 5447168
• 负责人: Dr. Anatole Neufeld
• 金额: --
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2004
• 资助国家: 德国
• 起止时间: 2003-12-31 至 2011-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/5447168?language=en
• 关键词: Ultrafast; reaction; dynamics; condensed; phase

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.

该项目的主要目标是从我们小组最近开发的一种新颖的量子经典方法开始，开发一个强大的框架，用于从头计算溶剂对反应动力学的影响。它具有明确的广泛的适用范围，并且没有标准混合方法固有的缺陷，如轨迹表面跳跃方案，平均场近似或量子经典Liouville方程。为此，我们计划使用几个参考模型来研究经典力学描述反应坐标的准确性和适用性，并基于经典自由度的从头算分子动力学描述，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开始实现可逆双相重组反应的非现象学建模，并探索非绝热反应中分支比的相干性和减相的作用。