Enhancement of Complexation due to the Effect of a Bath: A van der Waals Complex in N2 Bath

Abstract

In the present computational approach, the detail analysis of association followed by ensuing dissociation reaction of excited benzene (Bz) and hexafluorobenzene (HFB) system at 1000 K is performed in condensed phase system consisting of 1000 N2 molecules thermalized at 300 K. Appropriate approaches are adopted to analyse the trajectory results with some modification to the textbook concept and equations. Two N2 bath densities, namely, 20 and 324 kg/m3, are considered, and the results are compared with those obtained in vacuum. The results reveal that there is a change in impact parameters due to the collision with the bath molecules. One can correlate the impact parameter versus association probability relation in vacuum reaction to that of the condensed phase. Such a change of impact parameter in the condensed phase increases the association rate constant, while the collisional intermolecular energy transfer from the excited Bz-HFB complex to the bath decreases the dissociation rate. Overall, there is an enhancement of complexation due to the effect of the bath. The conclusion is made based on a total of 5100 trajectories in a condensed phase system.