Theory of electronically non-adiabatic chemical reactions: Quantum mechanical formulation of collinear reactions

Abstract

An electronically non-adiabatic collinear chemical reaction is investigated theoretically. The problem is formulated quantum mechanically in a close-coupling form by using a curvilinear coordinate system and an expansion in terms of vibrational wave functions. A rigorous expression for the non-adiabatic transition matrix is obtained in terms of the Green's function for the matrix operator. An adiabatic distorted wave approximation with respect to the electronic transition is discussed which incorporates the vibrational coupling and is expected to be a good approximation in low energy collisions. On the basis of this approximation, the mechanism of electronically non-adiabatic reactions is discussed qualitatively.

Work supported by the United States Air Force Office of Scientific Research, under Grant No. AFOSR-72-2272.

Work supported by the United States Air Force Office of Scientific Research, under Grant No. AFOSR-72-2272.

Notes

Work supported by the United States Air Force Office of Scientific Research, under Grant No. AFOSR-72-2272.

Additional information

Notes on contributors

H. Nakamura

On leave from Department of Applied Physics, University of Tokyo, Tokyo, Japan (present address).