Physical Chemistry Chemical Physics

Differential Shannon entropies and correlation measures for Born–Oppenheimer electron–nuclear dynamics: numerical results and their analytical interpretation

Peter Schürger, Volker Engel

Published Jan 1, 2023• 10 citations

Abstract

We study the Born-Oppenheimer dynamics within a model for a coupled electron-nuclear motion. Differential Shannon entropies are calculated from the time-dependent probability densities of the combined system and, using single particle densities, entropies for the electronic and nuclear degrees of freedom are derived. These functions provide information on details of the wave packet motion. From the entropies, we determine the mutual information which characterizes particle correlations. This quantity is compared to other measures of electron-nuclear entanglement. Numerical results are interpreted within an analytically solvable approach, and it is documented how these functions depend on properties of the Born-Oppenheimer wave function and, in particular, how dynamical effects like wave packet focusing and dispersion influence the correlation between the particles.

DOI: 10.1039/d3cp03573e

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