Quasiclassical dynamics of benzene overtone relaxation on an ab initio force field. I. Energy flow and survival probabilities in planar benzene for CH(v=2,3)

Abstract

Computational studies based upon ensembles of quasiclassical trajectories are presented for 21-mode (planar) benzene, with which we examined relaxation of the first and second (v=2,3) CH stretch overtones. The most complete ab initio force field available for this molecule was used for short time (t<240 fs) and long time (t=2.4 ps) dynamical calculations. Local mode analyses indicate that energy flow from the initially excited CH stretch is fast (t<240 fs) and irreversible. For both overtones examined, energy from the CH chromophore activates the following local modes in sequence: ipso in-plane CH wag, adjacent CC stretch, terminal CC stretch, ortho CH in-plane wag, meta CH in-plane wag, intermediate CC stretch, meta CH stretch, para CH in-plane wag, and para CH stretch. Long time calculations indicate that the in-plane CH wag and CH stretching local modes are at steady-state quantities by 2.4 ps, while the CC stretches and CCC bends continue to take on energy. The ortho and meta CH stretches were of minor importance in intramolecular vibrational energy redistribution in benzene, gaining little or no energy over the time scales we studied. Survival probabilities indicate that the half life of the excited CH stretch decreases by almost two thirds as the overtone energy is raised. The results of our study are compared to other classical and quantum dynamical investigations of benzene and are found to be in good qualitative agreement.