On-the-fly simulations of transient absorption pump–probe spectra: Combining mapping dynamics with doorway-window protocol
Abstract
We have constructed an ab initio protocol for the simulation of transient-absorption (TA) pump–probe (PP) signals of realistic polyatomic systems. The protocol is based on interfacing the doorway-window representation of spectroscopic signals with the on-the-fly mapping Hamiltonian dynamics approach at the symmetrical quasi-classical/Meyer–Miller level. The methodology is applied to the simulation of TA PP signals of two molecular systems, azobenzene and cis-hepta-3,5,7-trieniminium cation. For both molecules, the TA PP spectra were demonstrated to give a direct fingerprint of the excited state wavepacket dynamics and internal conversion, which permits the monitoring of the isomerization pathways en route to the final photoproducts.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (8)
Zhaofa Li
School of Chemistry, South China Normal University 1 , Guangzhou 510006,
Jiawei Peng
SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Environmental Theoretical Chemistry, School of Environment, South China Normal University 17 , Guangzhou 510006,
Yifei Zhu
Chao Xu
Liang Peng
Maxim F. Gelin
School of Science, Hangzhou Dianzi University 1 , Hangzhou 310018,
Feng Long Gu
MOE Key Laboratory of Environmental Theoretical Chemistry, South China Normal University 2 , Guangzhou 510006,
Zhenggang Lan
MOE Key Laboratory of Environmental Theoretical Chemistry, SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety, School of Environment, South China Normal University 3 , Guangzhou 510006,