Thermally averaged rate coefficients for vibrational state changes and dissociation from individual vibrational levels in H2-Ar collissions at 4500 K are derived from Monte Carlo quasiclassical trajectory calculations. The rate matrix is completed by linear surprisal interpolation. Relaxation times, induction times, and steady dissociation rates simulating a shock wave experiment are calculated by a matrix-eigenvalue solution of the master equation. Rotational equilibrium is assumed, but vibrational nonequilibrium effects are included in full. The resulting steady dissociation rates are only about 30% less than at equilibrium.
Bibliographical noteFunding Information:
This work was supported in part by the National Science Foundation under gram no_ CHE77-27415 and was aIso performed in part under the auspices of the United States Department of Energy_