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Electronic non-adiabatic states: towards a density functional theory beyond the Born–Oppenheimer approximation

Gidopoulos, N.I.; Gross, E.K.U.

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Authors

E.K.U. Gross



Abstract

A novel treatment of non-adiabatic couplings is proposed. The derivation is based on a theorem by Hunter stating that the wave function of the complete system of electrons and nuclei can be written, without approximation, as a Born–Oppenheimer (BO)-type product of a nuclear wave function, X(R), and an electronic one, ΦR(r), which depends parametrically on the nuclear configuration R. From the variational principle, we deduce formally exact equations for ΦR(r) and X(R). The algebraic structure of the exact nuclear equation coincides with the corresponding one in the adiabatic approximation. The electronic equation, however, contains terms not appearing in the adiabatic case, which couple the electronic and the nuclear wave functions and account for the electron–nuclear correlation beyond the BO level. It is proposed that these terms can be incorporated using an optimized local effective potential.

Citation

Gidopoulos, N., & Gross, E. (2014). Electronic non-adiabatic states: towards a density functional theory beyond the Born–Oppenheimer approximation. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 372(2011), Article 20130059. https://doi.org/10.1098/rsta.2013.0059

Journal Article Type Article
Online Publication Date Feb 10, 2014
Publication Date Mar 13, 2014
Deposit Date Sep 26, 2014
Publicly Available Date Oct 2, 2014
Journal Philosophical Transactions of the Royal Society of London A: Mathematical, Physical and Engineering Sciences.
Print ISSN 1364-503X
Electronic ISSN 1471-2962
Publisher The Royal Society
Peer Reviewed Peer Reviewed
Volume 372
Issue 2011
Article Number 20130059
DOI https://doi.org/10.1098/rsta.2013.0059
Keywords Beyond Born–Oppenheimer, Density functional theory, Non-adiabatic effects
Public URL https://durham-repository.worktribe.com/output/1420511

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