Energy sudden dissociative collisions: Structure and applications of factorization relations

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1985
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Chan, D.
Hoffman, David
Evans, James
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Ames LaboratoryPhysics and AstronomyMathematicsChemistry
Abstract

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 spectroscopicfactorization relations is straightforwardly extended here to ES dissociativecollisions. 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 oscillatorsystem. Relevance of these results to the prediction of (dissociative) state specific vibrational enhancement/inhibition is discussed.

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This article is published as Chan, C. K., D. K. Hoffman, and J. W. Evans. "Energy sudden dissociative collisions: Structure and applications of factorization relations." The Journal of chemical physics 82, no. 4 (1985): 1855-1865, doi:10.1063/1.448369. Posted with permission.

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Tue Jan 01 00:00:00 UTC 1985
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