Electronic non-adiabatic states

Abstract

A novel treatment of non-adiabatic couplings is proposed. The derivation starts from the long-known, but not well-known, fact that the wave function of the complete system of elctrons and nuclei can be written, without approximation, as a Born-Oppenheimer-type product of a nuclear wavefunction, X(R), and an electronic one, Phi_R(r), which depends parametrically on the nuclear configuration R. From the variational principle we deduce formally exact equations for Phi_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 wavefunctions and account for the electron-nuclear correlation beyond the Born-Oppenheimer level. It is proposed that these terms can be incorporated using an optimized local effective potential.