Temperature Dependence of the Vibrational Relaxation Rate Constants of CO2 (0001) in Binary Mixtures

The rate constants of intramolecular intermode relaxation of the CO₂ molecule (00⁰1) in pure CO₂ and in binary mixtures with He, Ar, H₂, O₂, N₂, CO, NO, N₂O, and H₂O were measured in the temperature range 300–1000 K by means of a laser-induced luminescence method. It is shown that these relaxation rate constants K for all the gas mixtures investigated increase with increase in the gas temperature in this range; the most efficient in deactivation of the 00⁰1 level are the collisions of CO₂ molecules with H₂O molecules; the mechanisms of relaxation of the 00⁰1 level of CO₂ and their channels depend not only on the temperature but also on the parameters of colliding particles; for each of the colliding partners of the CO₂ molecules there is a certain temperature T _c above which the temperature dependence of K is coordinated with the Landau–Teller dependence, and, moreover, the simpler the structure of the colliding partner of the CO₂ molecule, the higher the temperature T _c. Deviations from these dependences at temperatures T < T _c are attributed to the influence of intermolecular forces of attraction, change of relaxation channels, and formation of molecular clusters. For all the colliding partners of the CO₂ molecules, the interaction radii are determined from the intermolecular potentials of interaction used in the theoretical model.