AN ADVANCEMENT IN COMPUTATIONAL CHEMISTRY: QUANTUM-CLASSICAL DYNAMICS ON C5H4+

Abstract

The Time Dependent Discrete Variable Representation (TDDVR) method, a recently developed parallelized quantum-classical dynamical approach, is applied to the spectroscopically significant pentatetraene radical cation(PENT+), where multiple conical intersections exist in their five lowest excited electronic states, taking degeneracy among potential energy surfaces (PESs) into account, to illustrate their various dynamical aspects. In order to get UV photoelectron (PE) spectra, the associated Hamiltonian—where the Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) type interactions involved in those connected five electronic states—is subjected to first principles dynamics at the state-of-the-art level. Comprehensive analysis of the impact of these couplings on nuclear dynamics of the involved electronic states is done using the quantum-classical method, and the results are compared with those obserables derived from experiments.