The calculation of TV, VT, VV, VV′ - rate coefficients for the collisions of the main atmospheric components

Abstract

The first-order perturbation approximation is applied to calculate the rate coefficients of vibrational energy transfer in collisions involving vibrationally excited molecules in the absence of non-adiabatic transitions. The factors of molecular attraction, oscillator frequency change, anharmonicity, 3-dimensionality and quasiclassical motion have been taken into account in the approximation. The analytical expressions presented have been normalized on experimental data of VT-relaxation times in N₂ and O₂ to obtain the steric factors and the extent of repulsive exchange potentials in collisions N₂–N₂ and O₂–O₂. The approach was applied to calculate the rate coefficients of vibrational-vibrational energy transfer in the collisions N₂–N₂, O₂–O₂ and N₂–O₂. It is shown that there is good agreement between our calculations and experimental data for all cases of energy transfer considered.