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

Nikitas I. Gidopoulos, E. K.U. Gross*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

81 Scopus citations

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.

Original languageAmerican English
Article number20130059
JournalPhilosophical transactions. Series A, Mathematical, physical, and engineering sciences
Volume372
Issue number2011
DOIs
StatePublished - 13 Mar 2014
Externally publishedYes

Keywords

  • Beyond Born-Oppenheimer
  • Density functional theory
  • Non-adiabatic effects

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