Journal of Physical Chemistry A, Vol.105, No.47, 10646-10650, 2001
Gateway modes for collisional energy transfer between benzene and Ar
Quasiclassical trajectory calculations were used to explore the mechanism of collisional energy transfer between a benzene molecule and an Ar bath gas. Using single mode excitation, it was found that there are two factors that affect energy transfer: the frequency and the type of molecular motion that is associated with the mode. We find that the lowest frequency, out-of-plane torsion mode, is the gateway mode for energy transfer. When the same frequency is assigned also to the in-plane mode, the out-of-plane mode is still more efficient. Only when the frequencies of the out-of-plane and the in-plane modes are switched, the in-plane mode becomes the gateway mode for energy transfer. Therefore, the lowest the frequency is always the gateway mode, and given two modes of identical frequencies, the molecular motions determine the efficiency of energy transfer. These results agree with quantum calculations by Clary et al. [Clary et al. Faraday Discuss. 1995, 102, 423]. It is found that translation/rotation is a major channel of energy transfer and that vibration/translation energy transfer is efficiently mediated by rotations.