Document Type

Article

Department/Program

Physics

Journal Title

Journal of Chemical Physics

Pub Date

2-1979

Publisher

American Institute of Physics

Volume

70

Issue

4

Abstract

ABSTRACT A consistent general definition of diabatic representations has not previously been given, even though many practical examples of such representations have been constructed for specific problems. Such a definition is provided in this paper. Beginning with a classical trajectory formulation, we describe the form and behavior of velocity‐dependent couplings in slow collisions, including the effects of electron‐translation factors (ETF’s). We compare the couplings arising from atomic representations and atomic ETF’s with those arising from molecular representations and ’’switching function’’ ETF’s. We show that a unique set of switching functions makes the two descriptions identical in their effects. We then show that an acceptable general definition of a diabatic representation is provided by the condition P+A=0, where P is the usual nonadiabatic coupling matrix and A represents corrections to it arising from electron translation factors (ETF’s). Two distinct types of diabatic representation result, depending on the definition taken for A. States that undergo no deformation are called F diabatic; those that have no velocity‐dependent couplings are called M diabatic. Finally, we discuss the properties of representations that are partially diabatic and partially adiabatic, and we give some rules for the construction of representations that should be nearly optimal for describing many types of collision processes.

DOI

https://doi.org/10.1063/1.437650

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