The multistate multimode vibronic dynamics of benzene radical cation with a realistic model Hamiltonian using a parallelized algorithm of the quantumclassical approach

Abstract

We demonstrate the workability of a parallelized algorithm of the time-dependent discrete variable representation (TDDVR) method to explore the detailed dynamical aspects of vibronic interaction in two three-state model Hamiltonians (X²E_1g, B²E_2g, C²A_2u and (B²E_2g, D²E_1u, E²B_2u of benzene radical cation along with a preliminary investigation on its five electronic states (⁠ (X²E_1g, B²E_2g, C²A_2u,⁠ D²E_1u, E²B_2u). Since those electronic states are interconnected through a series of conical intersections, we have used six and nine vibronically important modes for the three- and five-state Hamiltonians, respectively, in order to perform the quantum dynamics on such system. The population profiles calculated by using our TDDVR approach show reasonably good agreement with the results obtained by exact quantum mechanical (multiconfiguration time-dependent Hartree) method, whereas the corresponding (calculated) photoabsorption spectra originating from various electronic states agree well with the experimental ones. It is important to note that the parallelized algorithm of our TDDVR approach reduces the computation cost by more than an order of magnitude compared to its serial analog. The TDDVR approach appears to be a good compromise between accuracy and speed for such large molecular system, where quantum mechanical description is needed in a restricted region.