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Quantum-Mechanical Transition-Complex Theory of Rearrangement Collisions

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.1701340· OSTI ID:4794538

The theory of rearrangement collisions is discussed in applications to bimolecular chemical reactions, using the method of stationary-state solutions to the Sunhrodinger equation to avoid the perplexities associated with the nonorthogonality of initial and final states. The analysis employed is originally due to Gerjuoy STAE. Gerjuay, Phys. Rev. 109: 1806(1958); Ann. Phys. (N.Y.) 5: 58(1958)!. The usual results of the formal theory of scattering, involving the transition matrix element, are derived, and a further explicit development of the theory is given which permits the use of a model Hamiltonian to represent the reacting system. Several alternate expressions are obtained for the transition matrix element, involving the use of the transition complex'' eigenfunctions as an approximate basis for expansion of the state vector; and an approximate expansion in ascending orders of virtual reactive scatterings'' is introduced as a method for rapidly expanding the state vector.

Research Organization:
Massachusetts Inst. of Tech., Cambridge
Sponsoring Organization:
USDOE
NSA Number:
NSA-16-028956
OSTI ID:
4794538
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 37; ISSN JCPSA6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
Country unknown/Code not available
Language:
English

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