Classical trajectory study of energy transfer in collisions of highly excited allyl radical with argon

Predicting the results of collisions of polyatomic molecules with a bath of atoms is a research area that has attracted substantial interest in both experimental and theoretical chemistry. Energy transfer, which is the consequence of such collisions, plays an important role in gas-phase kinetics and relaxation of excited molecules. We present a study of energy transfer in single collisions of highly vibrationally excited allyl radical in argon. We evolve a total of 52 000 classical trajectories on a potential energy surface, which is the sum of an ab initio intramolecular potential for the allyl and a pairwise interaction potential describing the argon's effect on the allyl. The former is described by means of a permutationally invariant full-dimensional potential, whereas the interaction potential between allyl and argon is obtained by means of a sum of pairwise potentials dependent on nonlinear parameters that have been fit to a set of MP2/avtz counterpoise corrected ab initio energies. Results are reported for energy transfers and related probability densities at different collisional energies. The sensitivity of results to the interaction potential is considered and the potential is shown to be suitable for future applications involving different isomers of the allyl. The impact of highly efficient collisions in the energy transfer process is examined. © 2013 American Chemical Society.