Compact and accurate ab initio valence bond wave functions for electron transfer: The classic but challenging covalent-ionic interaction in LiF

Abstract

The paper combines the valence bond block diabatization approach (VBBDA) with the idea of orbital breathing. With highly compact wave functions, the breathing orbital valence bond (BOVB) method is applied to investigate several atomic and molecular properties including the electron affinity of F, the adiabatic and diabatic potential energy curves and the dipole moment curves of the two lowest-lying 1Σ+ states, the electronic coupling curve and the crossing distance of the two diabatic states, and the spectroscopic constants of the ground states for LiF. The configuration selection scheme proposed in this work is quite general, requiring only the selection of several de-excitation and excitation orbitals in a sense like the restricted active space self-consistent field method. Practically, this is also the first time that BOVB results are extrapolated to complete basis set limit. Armed with the chemical intuition provided by VB theory, the classic but challenging covalent-ionic interaction in the title molecule is not only conceptually interpreted but is also accurately computed.