THEORY AND VALIDATION OF THE PHYSICALLY CONSISTENT COUPLED VIBRATION-CHEMISTRY VIBRATION MODEL

A consistent thermochemical relaxation model is presented that has bee n derived on the basis of T-vib.i-Boltzmann populated vibrational ener gy modes and truncated harmonic oscillators. A persistent application of these two assumptions to all types of chemical reactions with molec ular reactants leads to the coupled vibration-chemistry-vibration mode l (CVCV model), which specifies multiple temperature rate constants an d vibrational energies transferred due to chemical reactions in a cons istent way. The simple analytic expressions obtained for both rate con stants and transferred vibrational energies enable to account for ther mal 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 -selective model calculation and an experimental result.