Comparisons of classical and Wigner sampling of transition state energy levels for quasiclassical trajectory chemical dynamics simulations

摘要

Quasiclassical trajectory calculations are compared, with classical and Wigner sampling of transition state (TS) energy levels, for C2 H_5 F →HF+ C_2 H_4 product energy partitioning and [Cl CH3 Cl] - central barrier dynamics. The calculations with Wigner sampling are reported here for comparison with the previously reported calculations with classical sampling [Y. J. Cho, J. Chem. Phys. 96, 8275 (1992); L. Sun and W. L. Hase, J. Chem. Phys. 121, 8831 (2004)]. The C_2 H_5 F calculations were performed with direct dynamics at the MP~(2/6-)31 G level of theory. Classical and Wigner sampling give post-transition state dynamics, for these two chemical systems, which are the same within statistical uncertainties. This is a result of important equivalences in these two sampling methods for selecting initial conditions at a TS. In contrast, classical and Wigner sampling often give different photodissociation dynamics [R. Schinke, J. Phys. Chem. 92, 3195 (1988)]. Here the sampling is performed for a vibrational state of the ground electronic state potential energy surface (PES), which is then projected onto the excited electronic state's PES. Differences between the ground and the excited PESs may give rise to substantially different excitations of the vibrational and dissociative coordinates on the excited state PES by classical and Wigner sampling, resulting in different photodissociation dynamics.