Sensitivity of molecular vibrational dynamics to energy exchange rate constants

The sensitivity of molecular vibrational population dynamics, governing the CO laser operated in,fundamental and overtone transitions, to vibration-to-vibration rate constants is investigated. With this aim, three rate constant sets have been used, differing in their completeness (i.e. accounting for single-quantum exchange only, or for multi-quantum exchange with a limited number of rate constants obtained by semiclassical calculations, and, finally, with an exhaustive set of rate constants including asymmetric exchange processes, as well) and in the employed interaction potential. The most complete set,among these three is introduced in this paper. An existing earlier kinetic model was updated to include the latter new data., Comparison of data produced by kinetic modelling with the above mentioned sets of rate constants-shows that the vibrational distribution function, and, in particular, the CO overtone laser characteristics, are very sensitive to the choice of the model. The most complete model predicts slower evolution of the vibrational distribution, in qualitative agreement with experiments.