Semiclassical theory of vibrational, rotational and translational energy exchange in collisions of polyatomic molecules

Abstract

We derive a theory of inter- and intramolecular transfer of vibrational, rotational and translational energy in collisions of polyatomic molecules, in the case that only short range forces are important. Normal mode vibrations of molecules are treated quantum mechanically whereas translations and rotations are assumed to be classical degrees of freedom. We are able to show that, in case of short range forces, the energy exchange in binary collisions is essentially governed by an effective mass which is given by an algebraic function of the usual reduced mass and moments of inertia and depends also on the relative orientation of the two molecules. As an application of the theory, we calculated the probabilities for collision-induced 1 →0 transitions of the v 3 mode in pure CH3I, CH3Br and CH3Cl gases. The calculated values are close to the experimental vibrational deactivation probabilities.