Split Operator Method in MM-VB Model: Application to Non-adiabatic Dynamics Simulations
作者单位：Institute of Theoretical and Computational ChemistrySchool of Chemistry and Chemical Engineering Nanjing University
会议名称：《中国化学会第十二届全国量子化学会议》
会议日期：2014年
学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学]
摘 要：The mixed quantum/classical non-adiabatic dynamics simulations on the MM-VB model achieved great successful for the radiationless internal conversion processes of conjugated systems[1][2].In this non-adiabatic dynamics simulation,the total Hamiltonian is divided into a classical（nuclei）part and a quantum part（electron）.The nuclei move on a single adiabatic electronic potential energy surface（PES）following classical Newton equation,the PES is calculated on-the-fly by propagating the electronic wavefunction using time-dependent quantum *** convenient way of describing the non-adiabatic events around a conical intersection（CI）is through theTrajectory Surface Hopping（TSH）method,in which the switches between two adiabatic potential surfaces are controlled by the occupation probabilities in the non-adiabatic electronic wavefunction as time ***,in TSH approach,one critical issue is how to compute the time evolution of non-adiabatic electronic *** this work,the well-established split operator approximation method[3]is evaluated for its application in propagating the non-adiabatic *** will be highlighted for its high numerical precision comparable to the exact solution of the time-dependent Schr?dinger equation,while greatly cut down the time-cost,which could extend its capability to the system as large as 24π*** illustration,the radiationless 1Bu to 2Ag state conversion of mini-carotenoid has been systemically studied.