Theoretical studies of charge relaxation effects on the statics and dynamics of oxides

Abstract

Inclusion of spherical charge relaxation in response to the long-range electrostatic potential (potential induced breathing, or PIB) gives improved results for the static and dynamic properties of oxides. PIB is a Gordon-Kim type model, in which the crystal charge density is estimated by overlapping ionic charge densities. No experimental data are used, except for the values of universal constants, and in this sense the results are from first principles. In contrast to earlier models which include some form of charge relaxation, we explicitly include the breathing effects on the self-energy and pair potentials in the model Hamiltonian. PIB is a many-body effect that couples the long-and short-range forces in a way that is not present in any other first principles or empirical models. It leads to the observed violations of the Cauchy relations for the elastic constants whereas central force rigid ion models cannot violate the Cauchy relations. PIB also reduces the predicted LO-TO splitting because the breathing effect introduces dynamical effective charges that are lower in magnitude than the ionic charges. Some results are shown and discussed for MgO (periclase), BeO (bromellite), Al2O3 (corundum), TiO2 (rutile) and SiO2 (quartz and stishovite).