Inelastic Molecular Collisions with a Lennard-Jones (12–6) Interaction Energy

Abstract

Vibrational energy transfer is discussed for a Lennard‐Jones intermolecular interaction energy by use of the WKB semiclassical wavefunctions, from the point of view of the effect of an attractive term in the interaction energy. The effect is found to be very important in controlling the over‐all magnitude of the de‐excitation probability per unit time. An expression for fitting a Lennard‐Jones potential to an exponential potential is derived by comparing the leading terms in the exponent of the perturbation integral.