Vibration–vibration energy transfer in HF dimers

Abstract

A theory of vibration–vibration energy transfer is developed for hydrogen fluoride molecules based on the model of energy transfer through the interaction of H of one HF molecule with F of the other in a nonrigid hydrogen‐bond dimer. The theory is applied to HF(n)+HF(0) →HF(n−1)+HF(1)+ΔE for values of the vibrational quantum number up to 5. Calculations at 300 °K show the rapid energy exchange for these processes. Particularly fast rates are found for the collisions involving high vibrational states with small values of the energy mismatch. Reasonable agreement between the present theory and experiment is found for the deactivation processes with n=2, 3, 4, and 5.