On the calculation of time-dependent electron momenta within the Born-Oppenheimer approximation. 2019

Thomas Schaupp, and Volker Engel
Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Emil-Fischer-Str. 42, Würzburg 97074, Germany.

In the case of an adiabatic motion in molecules, electrons adjust to the smoothly changing geometry of the nuclei. Although then the Born-Oppenheimer (BO) approximation is valid, it fails in predicting the time-dependence of electron momenta because, within its product ansatz for the wave function, the respective expectation values are zero. It is shown that this failure can be circumvented using the Ehrenfest theorem. Here we extend our former work [T. Schaupp et al., Eur. Phys. J. B 91, 97 (2018)] and regard models in higher dimensions and for more particles. We solve the time-dependent Schrödinger equation for the combined nuclear-electronic motion and compare the results to those derived from BO wave functions. For all situations, it is found that the time-dependent BO electronic momenta are in excellent agreement with the numerically exact results.

UI MeSH Term Description Entries

Related Publications

Thomas Schaupp, and Volker Engel
October 2016, The journal of physical chemistry. A,
Thomas Schaupp, and Volker Engel
March 2008, The Journal of chemical physics,
Thomas Schaupp, and Volker Engel
January 1990, Physical review. D, Particles and fields,
Thomas Schaupp, and Volker Engel
June 2015, The journal of physical chemistry. A,
Thomas Schaupp, and Volker Engel
May 2020, The journal of physical chemistry letters,
Thomas Schaupp, and Volker Engel
March 2016, The journal of physical chemistry. B,
Thomas Schaupp, and Volker Engel
November 1985, Physical review letters,
Thomas Schaupp, and Volker Engel
June 1987, Physical review. A, General physics,
Thomas Schaupp, and Volker Engel
January 2017, Journal of chemical theory and computation,
Copied contents to your clipboard!