Temperature dependence of the probability of vibration-vibration-rotation energy transfer in HCl (v = 2) + HCl (v = 0) ⇋ HCl (v = 1) + HCl (v = 1)

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Abstract
Energy transfer probabilities for the vibration‐vibration process HCl(v = 2) + HCl(v = 0)⇄HCl(v = 1) + HCl(v = 1) + ΔE = 102 cm−1 have been calculated in the temperature range of 300–1000°K assuming that ΔE is supplied or removed through the vibration‐rotation process. The interaction potential is assumed as the sum of repulsive, attractive, dipole‐dipole, and hydrogen‐bond energy terms. It is shown that the probability decreases nearly linearly with rising temperature between 300–600°K; this result agrees with experiment. After reaching a minimum value at 700°K, the probability increases with temperature. The temperature dependence is explained in terms of the contribution of molecular attractions including dipole‐dipole and hydrogen‐bond terms and the effect of translational motion on the vibration‐rotation process.