Concept of Intermolecular Forces in Collisions

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Abstract
For polar or electronically excited molecules the concept of intermolecular forces requires clarification. To calculate the equation of state or equilibrium properties, it suffices to use intermolecular forces which are averaged over the magnetic quantum numbers, but for nonequilibrium or transport properties it is necessary to know the intermolecular energy for each separate quantum state. There are many different representations of intermolecular forces, depending on which degrees of freedom are treated quantum mechanically and which classically. The whole concept of intermolecular force becomes nebulous when a large fraction of the collisions are not adiabatic.

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