Energy transfer in intermolecular collisions of polycyclic aromatic hydrocarbons with bath gases He and Ar.

Abstract

Classical trajectory simulations of intermolecular collisions were performed for a series of polycyclic aromatic hydrocarbons interacting with the bath gases helium and argon for bath gas temperature from 300 to 2500 K. The phase-space average energy transferred per deactivating collision, ⟨∆Edown⟩, was obtained. The Buckingham pairwise intermolecular potentials were validated against high-level quantum chemistry calculations and used in the simulations. The reactive force-field was used to describe intramolecular potentials. The dependence of ⟨∆Edown⟩ on initial vibrational energy is discussed. A canonical sampling method was compared with a microcanonical sampling method for selecting initial vibrational energy at high bath gas temperatures. Uncertainties introduced by the initial angular momentum distribution were identified. The dependence of the collisional energy transfer parameters on the type of bath gas and the molecular structure of polycyclic aromatic hydrocarbons was examined.