Rate constant of VT/VV energy exchange in the collision of di- and polyatomic molecules within the SFO model

Abstract

The numerical-analytical investigation of the shock forced oscillator (SFO) model is complete. Approaches for calculating the probabilities of quantum transitions from the initial to some final state with VV energy exchange of diatomic molecules and VV and VT energy exchange of polyatomic molecules are considered. Formulas for calculating the probabilities of the \({W_{{i_1},{i_2} \to {f_1},{f_2}}}\) transition for VV energy exchange in collision of molecules AB and CD within the harmonic approximation are represented (SFHO model). It is shown that the probabilities of a quantum transition in VV and VT energy exchange of polyatomic molecules can be calculated in terms of the quantum transition probability for VT energy exchange of diatomic molecules on the assumption of “frozen” quantum transitions of polyatomic molecules. The problem of determining the dissociation rate constant is considered by the example of a nitrogen molecule (N2) in the N2–N2 system for the “improved” Lennard-Jones potential in VV energy exchange. The calculated dissociation rate constant is compared with the experimental data obtained for a shock tube.