Vibrational energy transfer in non-reactive molecular collisions: An information-theoretic analysis

Experimental and (trajectory) computed rates of vibrational relaxation of molecules in selected internal states are analyzed. A dynamic constraint is identified. The entire array of (vibrational) manifold-to-manifold rate constants (at a given temperature) is shown to be characterized by this constraint and hence yield a linear surprisal plot. It is argued that bulk measurements of the vibrational relaxation time in a buffer gas will suffice to determine the single parameter in the dynamic constraint.