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Semiclassical theory of vibrational energy relaxation

Robert Karrlein, Hermann Grabert

physics.chem-pharXiv:physics/9711028

Abstract

A theory of vibrational energy relaxation based on a semiclassical treatment of the quantum master equation is presented. Using new results on the semiclassical expansion of dipole matrix elements, we show that in the classical limit the master equation reduces to the Zwanzig energy diffusion equation. The leading quantum corrections are determined and discussed for the harmonic and Morse potentials.

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