Electronic Flux Density beyond the Born-Oppenheimer Approximation

Axel Schild*, Federica Agostini, E. K.U. Gross

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

37 Scopus citations

Abstract

In the Born-Oppenheimer approximation, the electronic wave function is typically real-valued and hence the electronic flux density (current density) seems to vanish. This is unfortunate for chemistry, because it precludes the possibility to monitor the electronic motion associated with the nuclear motion during chemical rearrangements from a Born-Oppenheimer simulation of the process. We study an electronic flux density obtained from a correction to the electronic wave function. This correction is derived via nuclear velocity perturbation theory applied in the framework of the exact factorization of electrons and nuclei. To compute the correction, only the ground state potential energy surface and the electronic wave function are needed. For a model system, we demonstrate that this electronic flux density approximates the true one very well, for coherent tunneling dynamics as well as for over-the-barrier scattering, and already for mass ratios between electrons and nuclei that are much larger than the true mass ratios.

Original languageAmerican English
Pages (from-to)3316-3325
Number of pages10
JournalJournal of Physical Chemistry A
Volume120
Issue number19
DOIs
StatePublished - 19 May 2016
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

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