Theory and validation of the physically consistent coupled vibration-chemistry-vibration model

A consistent thermochemical relaxation model is presented that has been derived on the basis of 7\ ib,Boltzmann populated vibrational energy modes and truncated harmonic oscillators. A persistent application of these two assumptions to all types of chemical reactions with molecular reactants leads to the coupled vibrationchemistry-vibration model (CVCV model), which specifies multiple temperature rate constants and vibrational energies transferred due to chemical reactions in a consistent way. The simple analytic expressions obtained for both rate constants and transferred vibrational energies enable to account for thermal nonequilibrium not only in dissociation, but also in exchange and associative ionization reactions. The model assumptions as well as the introduced model parameters are evaluated by comparisons with a state-selectiv e model calculation and an experimental result.

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