Nonequilibrium velocity distribution and dissociation rate in dissociation of diatomic molecules

The nonequilibrium velocity distribution and dissociation rate in the dissociation of diatomic molecules in a heat bath of inert atoms are studied by solving the Boltzmann equation with the Monte Carlo simulation. The explicit time‐dependent velocity distribution and dissociation rate from the initial equilibrium to the quasisteady state are obtained for the dissociation model, where the vibrational distribution is taken to be the Boltzmann equilibrium distribution; the effects of the vibrational transition are taken into account by a simplified model, and the cross section is taken to be a hard sphere model with the line‐of‐centers dissociation cross section. The quasisteady state velocity distributions and dissociation rates of upper vibrational levels, from which the dissociation occurs effectively, indicate significant deviations from equilibrium. The decreases in the dissociation rates of the upper vibrational levels from the equilibrium dissociation rates amount to 75% for H2–Ar and 20% for N2 or O2...

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