Pressure Effects on the Relaxation of an Excited Ethane Molecule in High-Pressure Bath Gases

Abstract

We use molecular dynamics to calculate the rotational and vibrational energy relaxation of C2H6 in Ar, Kr, and Xe bath gases over a pressure range of 10–400 atm and at temperatures of 300 and 800 K. The C2H6 is instantaneously excited by 80 kcal/mol randomly distributed into both vibrational and rotational modes. The computed relaxation rates show little sensitivity to the identity of the noble gas in the bath. Vibrational relaxation rates show a nonlinear pressure dependence at 300 K. At 800 K the reduced range of bath gas densities covered by the range of pressures does not yet show any nonlinearity in the pressure dependence. Rotational relaxation is characterized with two relaxation rates. The slower rate is comparable to the vibrational relaxation rate. The faster rate has a linear pressure dependence at 300 K but an irregular, nonlinear pressure dependence at 800 K. To understand this, a model was developed based on approximating the periodic box used in the molecular dynamics simulations by an equal-volume collection of cubes where each cube is sized to allow only single occupancy by the noble gas or the molecule. Combinatorial statistics then leads to a pressure- and temperature-dependent analytic distribution of the bath gas species the molecule encounters in a collision. This distribution, the dissociation energy of molecule/bath gas complexes and bath gas clusters, and the computed energy release per collision combine to show that only at 300 K is the energy release sufficient to dissociate likely complexes and clusters. This suggests that persistent and pressure-dependent clusters and complexes at 800 K may be responsible for the nonlinear pressure dependence of rotational relaxation.

An advanced bath model to simulate association followed by ensuing dissociation dynamics of benzene + benzene system: a comparative study of gas and condensed phase results

“…One additional phenomenon that is present in condensed phase calculation is collisional intermolecular energy transfer (CIET), which has been a topic of research over the years due to its applicability in chemical reactions and atmospheric chemistry. 46,47,[49][50][51][60][61][62][63][64][65][66][67][68][69][70] Theoretically, the master equation model, 61,[66][67][68][69][70] and bath model, 46,47,[49][50][51] have successfully encountered the intermolecular energy transfer phenomena in the past. In the present work, CIET may play a decisive role in the difference in association rates between gas and condensed phase dynamics.…”