Optical properties of LiF

Abstract

In this paper, we examine the optical properties of LiF. The fundamental calculations performed are a self-consistent Hartree-Fock band-structure calculation. As has been found previously, such a calculation has substantial errors when compared with experiment. Correlation corrections are needed and are included by means of the electronic-polaron method. The usual electronic polaron is extended to include short-range polarization corrections which the usual model neglects but which are peculiarly large for LiF. The energy bands are evaluated directly by the linear-combination-of-local-basis-functions method along with the crystal wave functions for 89 points in the irreducible wedge of the first Brillouin zone. Using these results and the Lemann-Taut interpolation scheme the density of states, the joint density of states, and the imaginary part of the dielectric function are computed. These results which neglect the formation of excitons and "plasmons" are in poor agreement with experiment. The effect of the exciton formation is included by a Koster-Slater one-band—one-site calculation. We find that the inclusion of exciton effects substantially improves the level of agreement with experiment. This is in direct contrast with recent work of Menzel et al. in which energy-band theory alone is found to account for the optical properties of LiF. This disagreement is discussed in detail.