A quantum-classical approach to the molecular dynamics of butatriene cation with a realistic model Hamiltonian

Abstract

We are investigating the molecular dynamics of the butatriene cation after excitation from the ground state (X²B_2g) to the first excited electronic state (A²B_2u) by using the time-dependent discrete variable representation (TDDVR) method. The investigation is being carried out with a realistic 18-mode model Hamiltonian consisting of all the vibrational degrees of freedom of the butatriene molecule. First, we perform the simulation on a basic five mode model, and then by including additional thirteen modes as bath on the basic model. This sequential inclusion of bath modes demonstrates the effect of so called weak modes on the subsystem, where the calculations of energy and population transfer from the basic model to the bath quantify the same effect. The spectral profile obtained by using the TDDVR approach shows reasonably good agreement with the results calculated by the quantum mechanical approach/experimental measurement. 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.