Abstract

Thermally averaged rate coefficients for vibrational state changes and dissociation from individual vibrational levels in H 2-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.

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