项目名称: 振转激发的影响:多通道化学反应体系的准经典轨线研究
项目编号: No.21303217
项目类型: 青年科学基金项目
立项/批准年度: 2014
项目学科: 数理科学和化学
项目作者: 曹剑炜
作者单位: 中国科学院化学研究所
项目金额: 25万元
中文摘要: 对多通道反应进行量子态层次研究是分子反应动力学领域的前沿课题。目前振转激发对多通道化学反应体系的影响有待探索。本项目中,我们拟选择H+SiH4,H+Si2H6和F+SiH4等多通道多原子反应体系为研究对象,以准经典轨线方法为基础,从发展方法和具体应用两方面致力于研究以下问题:(i)精确计算轨线中多原子分子振动量子数,并发展有效降低计算量同时充分考虑量子化约束的Gaussian binning方法;(ii)多原子体系中Polanyi法则的适用性;(iii)振转激发下,体系中不同反应通道之间的相互竞争机制。这些研究一方面将扩展准经典轨线方法在多原子态态反应动力学研究中的应用;另一方面可以揭示不同振动和转动激发对所研究反应体系的影响,深化对多原子微观反应动力学的认识。
中文关键词: 反应动力学;原子水平机理;振动激发;;
英文摘要: Quantum-state resolved dynamics of multichannel reactions is a frontier of the molecular reaction dynamics research. The influence of vibrational and rotational excitation to the multichannel chemical system is not clear nowadays. We would perform the quasiclassical trajectory (QCT) simulations to research the vibrational and rotational excitation dynamics of H+SiH4, H+Si2H6 and F+SiH4 reactions and focus on both the method development and applications involving:(i)The exact assignment of quantum states for polyatomic products in trajectories, and the strategy to save computation and fully incorporate the "quantum spirit" in Gaussian binning procedure; (ii) The applicability of Polanyi rules in polyatomic system; (iii) The competing mechanisms between the different reaction channels of the polyatomic system with the reactant vibrationally and rotationally excited. The use of QCT method will be extended to polyatomic state-to-state dynamics studies, and the influence of different vibrational and rotational excitations will be revealed. It would be beneficial for understanding the quantum-state resolved dynamics of polyatomic reactions.
英文关键词: reaction dynamics;atomic-level mechanism;vibrational excitation;;