How to calculate linear absorption spectra with lifetime broadening using fewest switches surface hopping trajectories: A simple generalization of ground-state Kubo theory

作者：Petit Andrew S^*; Subotnik Joseph E

来源：Journal of Chemical Physics, 2014, 141(1): 014107.

DOI：10.1063/1.4884945

In this paper, we develop a surface hopping approach for calculating linear absorption spectra using ensembles of classical trajectories propagated on both the ground and excited potential energy surfaces. We demonstrate that our method allows the dipole-dipole correlation function to be determined exactly for the model problem of two shifted, uncoupled harmonic potentials with the same harmonic frequency. For systems where nonadiabatic dynamics and electronic relaxation are present, preliminary results show that our method produces spectra in better agreement with the results of exact quantum dynamics calculations than spectra obtained using the standard ground-state Kubo formalism. As such, our proposed surface hopping approach should find immediate use for modeling condensed phase spectra, especially for expensive calculations using ab initio potential energy surfaces.

• 出版日期2014-7-7