CH_2NH_2^+体系在高激发态上的非绝热动力学理论研究（英文）  

Theoretical Studies of Nonadiabatic Dynamics on High-LyingExcited States of CH_2NH_2^+

作　　者：江圣世 谢宇[2] 任伟康 袁峰[1] 

机构地区：[1]青岛大学物理科学学院,青岛266071 [2]中国科学院青岛生物能源与过程研究所生物基材料重点实验室,青岛266101

出　　处：《青岛大学学报（自然科学版）》2017年第1期29-34,共6页Journal of Qingdao University(Natural Science Edition)

基　　金：国家自然科学基金(批准号:21503248)资助

摘　　要：CH_2NH_2^+对于理解分子的光激发问题来说是一个典型的分子体系。到目前为止,关于CH_2NH_2^+的非绝热动力学理论研究大部分都集中在它从低激发态出发的动力学上。然而,更高的激发应该也会对CH_2NH_2^+的动力学有潜在的影响。因此,在本次工作中,用即时轨线面跳跃(TSH)方法,在含时密度泛函层面上研究了CH_2NH_2^+分子体系从高激发态上出发的非绝热动力学。通过TSH方法,模拟了从单重激发态(S3/S4/S5)出发的动力学。动力学结果分析表明CN和CH/NH的解离很难同时发生。随着激发态的升高,CH/NH解离的增多导致了体系能量的减少并且使CN键解离减少。另外,扭转运动在从高激发态出发的TSH动力学中并不占主导地位。Methaniminium cation（CH2NH2＋）is a typical molecular system for understanding the photoexcitation.So far,theoretical studies of nonadiabatic dynamics on CH2NH2＋mostly focused on its dynamics starting from the low-lying excited states.However,the higher excitation should also have potential influence on the dynamics of CH2NH2＋.Thus,the nonadiabatic dynamics of CH2NH2＋molecular system starting from the high-lying excited states is studied by using the on-the-fly trajectory surface-hopping（TSH）approach at the TDDFT level in this work.Through the TSH method,the dynamics with the starting on the singlet excited states（S3/S4/S5）are simulated.The analysis of dynamic results shows that the dissociations of CN and CH/NH hardly occur at the same time.Along with becoming higher of excited state,the increasing of dissociations’number of the CH/NH induces the decrease of system’s energy and fewer dissociations of CN bond.And the torsional motions are not dominant in the TSH dynamics from the high-lying excited states.

关 键 词：面跳跃 非绝热动力学 CH2NH2+ 

分 类 号：O413.2[理学—理论物理] O641.121[理学—物理]