Ground- and excited-state properties of LiF in the local-density formalism

Abstract

The band structure, charge density, x-ray scattering factor (and their behavior under pressure), equilibrium lattice constant, and cohesive energy of the prototype ionic solid LiF were determined using our recently developed self-consistent numerical basis set (non-muffin-tin) linear-combination-of-atomic-orbitals method, within the local-density formalism (LDF). The details of the bonding and the effects of exchange and correlation on the electronic structure are discussed with reference to the conventional picture of ionic bonding. Remarkably good agreement is found with the observed data for the ground-state properties of the system. Contrary to the results of previous band studies, the conventional band-structure approach to excitation energies (i.e., identifying them with the band eigenvalue differences) is found to fail completely in accounting for the observed data in the entire x-ray and optical spectral region when fully self-consistent solutions of the LDF one-particle equation with no further approximation to the crystal potential are obtained. It is found that in the presence of some spatial localization of the initial or final crystal states, the spurious self-interaction terms, as well as the polarization and orbital relaxation self-energy effects are of a similar order of magnitude as the Koopmans'-like interband terms. In order to treat these effects within the LDF self-consistently, we describe the excitation processes as transitions involving point-defect-like states in the solid calculated by a supercell method in which the excitation energies are determined as total-energy differences between (separately calculated) excited- and ground-state configurations. The excited state is represented as a superlattice of locally excited sites using large (8-and 16-atom) unit cells, each containing a single excited site. We find, in the self-consistency limit, that a small but finite degree of spatial localization of the excited states exists even for valence excitations, inducing thereby self-interaction as well as self-energy relaxation and polarization effects. The LDF model is found to account very well for both interband and exciton transitions over the entire spectral region (12-695 eV) and to yield definite predictions regarding the exciton bandwidths and series limits.