Chitsazi, Rezvan; Wagner, Albert
Quasi-classical molecular dynamics simulations were used to study the energy relaxation of an initially non-rotating, vibrationally excited (nu = 4) hydroxyl radical (OH) in an Ar bath at 300 K and at high pressures from 50 atm to 400 atm. A Morse oscillator potential represented the OH, and two sets of interaction potentials were used based on whether the Ar-H potential was a Buckingham (Exp6) or a Lennard-Jones (LJ) potential. The vibrational and rotational energies were monitored for 25 000-90 000 ps for Exp6 trajectories and 5000 ps for LJ trajectories. Comparisons to measured vibrational relaxation rates show that Exp6 rates are superior. Simulated initial vibrational relaxation rates are linearly proportional to pressure, implying no effect of high-pressure breakdown in the isolated binary collision approximation. The vibrational decay curves upward from single-exponential decay. A model based on transition rates that exponentially depend on the anharmonic energy gap between vibrational levels fits the vibrational decay well at all pressures, suggesting that anharmonicity is a major cause of the curvature. Due to the competition of vibration-to-rotation energy transfer and bath gas relaxation, the rotational energy overshoots and then relaxes to its thermal value. Approximate models with adjustable rates for this competition successfully reproduced the rotational results. These models show that a large fraction of the vibrational energy loss is initially converted to rotational energy but that fraction decreases rapidly as the vibrational energy content of OH decreases. While simulated rates change dramatically between Exp6 and LJ potentials, the mechanisms remain the same. Published under license by AIP Publishing.