AbstractThe electronic structure of F, H, Vk centres in a LiF crystal is calculated using the INDO semiempirical method. Use of both, the modified calculating scheme and earlier derived parameters permit to reproduce quite well optical absorption energies for hole centres and confirm their model of F molecular ion in a crystal. The locations of defect levels with respect to the band edges of a perfect LiF crystal are discussed. The calculations of pairs of nearest F–H, F–Vk centres predict energies of their radiative tunneling recombination of about 1 and 1.4 eV, respectively.