Estimation of exponentially small overlap integrals in the framework of phase space distributions

Alexey V. Sergeev and Bilha Segev

Department of Chemistry, Ben-Gurion University of the Negev
POB 653, Beer-Sheva 84105, Israel

The integral $\int d\vec{q} \psi_0(\vec{q}) \psi_1(\vec{q})$ where $\psi_0(\vec{q})$ is the ground state eigenfunction of a Hamiltonian $H_0$, and $\psi_1(\vec{q})$ is the eigenfunction of the highly excited state of a Hamiltonian $H_1$ corresponding to some energy $E$ is estimated by replacing the eigenfunctions by their Wigner functions, and by analyzing the phase space integral. In the quasiclassical limit only a vicinity of one point where $H_1(\vec{q},\vec{p})=E$ and where the Wigner function $\rho_1(\vec{q},\vec{p})$ is maximal contributes to the integral [1, 2]. Results are illustrated for Morse and Poescl - Teller oscillators.

1. Segev B. and Heller E. J. Phase-space derivation of propensity rules for energy transfer processes between Born-Oppenheimer surfaces. J. Chem. Phys. 112, 4004 (2000).

2. Sergeev A. V. and Segev B. Most probable path in phase space for a radiationless transition in a molecule. J. Phys. A: Math. Gen. (2002).

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Designed by A. Sergeev.