ELECTRONIC-STRUCTURE OF SILVER-HALIDES

The electronic structure of the silver halides AgCl, AgBr and AgI is c alculated within the local density approximation using a pseudopotenti al, plane-wave method. When we compare the calculated densities of sta tes with photoemission experimental data, we find that the silver 4d-s tates are too high in energy. An analysis of the atomic eigenvalues of the silver 4d-states and the halogen valence p-states as a function o f occupation and of their respective ionization energies indicates tha t this error is in part due to the failure of the local-density approx imation and in part due to the identification of Kohn-Sham eigenvalues with removal energies. These errors can be traced as self-interaction errors that are larger for the silver d states than for the halogen p -states. (C) 1998 Published by Elsevier Science Ltd.