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

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, Φ R ( r ), which depends parametrically on the nuclear configuration R . From the variational principle, we deduce formally exact equations for Φ R ( 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.