Energy sudden dissociative collisions: Structure and applications of factorization relations

In the energy sudden (ES) approximation for nonreactive molecular collisions, there exist factorization relations by which an arbitrary T‐matrix element can be predicted as a spectroscopic linear combination of those out of some other, input state. These were first discovered for ground state input but this restriction was later removed. This general form of the spectroscopic factorization relations is straightforwardly extended here to ES dissociative collisions. One finds that in predicting dissociation amplitudes out of some state, it is necessary to use input data out of a higher (energy) bound state. Thus ground state factorization relations cannot be used. The structure of two natural forms of the factorization relation coefficients (equivalent by virtue of ES consistency conditions among T‐matrix elements out of a single state) are analyzed in detail for a collinear atom‐truncated square‐well diatomic oscillator system. Relevance of these results to the prediction of (dissociative) state specific vibrational enhancement/inhibition is discussed.