Theoretical study of curve crossing: ab initio calculations on the four lowest 1Σ+ states of LiF

Abstract

The potential curves of the four lowest 1Σ+ states of LiF have been studied by ab initio configuration interaction methods, using a contracted Gaussian basis set of better than double-ζ quality, augmented with diffuse basis functions on the fluorine atom. The choice of orbitals and selection of configurations were carried out with the objective of obtaining a balanced treatment of the four states and of the different regions of the potential curves. ``Generalized valence-bond'' orbitals, obtained from ground-state MCSCF calculations, together with ``improved virtual orbitals,'' were found suitable for the construction of the configuration functions. The latter were energy selected from all single and double excitations relative to a set of 12 ``reference configurations,'' chosen to include all contributions found important for any of the four states at any internuclear distance. The expected avoided crossing between the lowest covalent and ionic structures is found at an internuclear distance of about 11 bohr, compared to the experimentally deduced value of 14 bohr, due to the considerable difficulty in obtaining a balanced description of the electron correlation of the separated species, particularly the F− ion. A set of diabatic potential curves was generated from the two lowest adiabatic curves by a novel procedure based on the Rittner model of the ionic state. A set of adjusted adiabatic potentials was obtained from the diabatic curves after shifting the ionic diabatic curve downward by 0.42 eV to correct for the error in the computed electron affinity of the fluorine atom, resulting in a shift of the avoided crossing to the correct internuclear distance of 14 bohr. The dipole moments of the four states were computed as a function of internuclear distance and were interpreted in terms of the electronic structure.