A Competition between Dissociation Pathway and Energy Transfer Pathway: Unimolecular Dissociation of a Benzene-Hexafluorobenzene Complex in Nitrogen Bath.

Abstract

The unimolecular dissociation of a benzene-hexafluorobenzene complex at 1000, 1500, and 2000 K is studied inside a bath of 1000 N2 molecules kept at 300 K using chemical dynamics simulation. Three bath densities of 20, 324, and 750 kg/m3 are considered. The dissociation dynamics of the complex at a 20 kg/m3 bath density is found to be similar to that in the gas phase, whereas the dynamics is drastically different at higher bath densities. The microcanonical/canonical dissociation rate constants for the three bath densities are calculated and fitted to the Arrhenius equation. The activation energies are found to be similar to the gas-phase one. However, the pre-exponential factor is lower and decreases with the increase in bath density. The vibrational degree of freedom of the complex more effectively participates in the collisional energy transfer to the N2 bath, whereas the translational and rotational degrees of freedom of N2 receive the transferred energy. The energy transfer efficiency increases with the increase in bath density. The time scale of the energy transfer pathway is more than that of the dissociation pathway, and negligible direct dissociation of the complex is observed from the simulation at the highest bath density.