Multi-state multi-mode nuclear dynamics on three isomers of C6H4F +2 using parallelized TDDVR approach

We have performed molecular dynamics on the three isomers of the difluorobenzene radical cation (C6H4F+2) after excitation from the ground state to a specific higher electronically excited state by using our recently implemented parallelized Time-Dependent Discrete Variable Representation (TDDVR) methodology. A five-state eleven-mode realistic model Hamiltonian for o-C6H4F+2 and two separate five-state ten-mode Hamiltonians for m- and p-isomer of the same radical cation are considered, where those five electronic states are interconnected through several conical intersections in the vicinity of the Franck–Condon (FC) region and thus the dynamics for each case become complex. The photoelectron, mass analyzed threshold ionization spectra and population profiles obtained by using our TDDVR approach show reasonably good agreement with the results obtained by multiconfiguration time dependent Hartree (MCTDH) method. It is worthwhile to mention that the parallelized TDDVR algorithm reduces the computation time by more than an order of magnitude compared to its serial analog and, therefore, such approach appears to be a good compromise between accuracy and speed for a large molecular system.