A quantum-classical approach to the molecular dynamics of pyrazine with a realistic model Hamiltonian.
We investigate the molecular dynamics of pyrazine after excitation to the S2 electronic state by using the time-dependent discrete variable representation (TDDVR) method. The investigation has been carried out with a realistic 24-mode model Hamiltonian consisting of all the vibrational degrees of freedom of pyrazine molecule. First, we perform the simulation on a basic four-mode model, and then by including additional eight important modes and finally, by introducing 20 bath modes on the basic model. This sequential inclusion of bath modes demonstrates the effect of weak modes on the subsystem, where the calculations of energy and population transfer from basic model to the bath quantify the same effect. The spectral profile obtained by using TDDVR approach shows reasonably good agreement with the results calculated by quantum mechanical approach. It appears that the TDDVR approach for those large systems where quantum mechanical description is needed in a restricted region is a good compromise between accuracy and speed.
Puzari
Panchanan
P
Department of Chemistry, Indian Institute of Technology, Guwahati, North Guwahati, Guwahati 781 039, India.
Sarkar
Biplab
B
Adhikari
Satrajit
S