A quantum-classical approach to the photoabsorption spectrum of pyrazine

Abstract

We have used the time-dependent discrete variable representation (TDDVR) method to simulate the photoabsorption spectrum of pyrazine. The time-dependent molecular dynamics of pyrazine after excitation to the S₂ electronic state is considered as a benchmark to investigate the S₂ absorption spectrum. We have carried out the dynamics on a basic four-mode model of pyrazine with the inclusion of five major modes as well as the rest of the vibrational modes as bath modes. Investigations reveal the effect of bath modes such as energy and population transfer from the subsystem to the bath. Calculated results demonstrate excellent agreement with traditional quantum-mechanical findings during the entire propagation and converge to the exact quantum results when enough gridpoints are used. It appears that TDDVR, as a numerical quantum dynamics methodology, is a good compromise between accuracy and speed.