Li, C., Requist, R., Gross, E. K. U.

Density functional theory of electron transfer beyond the Born-Oppenheimer approximation: Case study of LiF
Journal of Chemical Physics **148**, (8),pp 084110/1-10 (2018)
We perform model calculations for a stretched LiF molecule, demonstrating that nonadiabatic charge transfer effects can be accurately and seamlessly described within a density functional framework. In alkali halides like LiF, there is an abrupt change in the ground state electronic distribution due to an electron transfer at a critical bond length R = R_{c}, where an avoided crossing of the lowest adiabatic potential energy surfaces calls the validity of the Born-Oppenheimer approximation into doubt. Modeling the R-dependent electronic structure of LiF within a two-site Hubbard model, we find that nonadiabatic electron-nuclear coupling produces a sizable elongation of the critical R_{c} by 0.5 bohr. This effect is very accurately captured by a simple and rigorously derived correction, with an M^{−1} prefactor, to the exchange-correlation potential in density functional theory, M = reduced nuclear mass. Since this nonadiabatic term depends on gradients of the nuclear wave function and conditional electronic density, ∇_{RX}(R) and ∇_{R}n(r, R), it couples the Kohn-Sham equations at neighboring R points. Motivated by an observed localization of nonadiabatic effects in nuclear configuration space, we propose a local conditional density approximation - an approximation that reduces the search for nonadiabatic density functionals to the search for a single function y(n).

TH-2018-09