Relativistic AB Initio calculations of the properties of ionic solids

Abstract

Relativistic ab initio calculations of inter-ionic potential energies are used to develop a reliable non-empirical method for predicting the properties of ionic solids containing the heaviest ions. A physically realistic method for describing the non-negligible differences between free and in-crystal ion wavefunctions is described. Functions are presented for describing the partial quenching, arising from ion wavefunction overlap, of the standard long-range form of the inter-ionic dispersive attractions. These attractions are shown to be distinct from the contributions to the inter-ionic potentials that arise from that portion of the electron correlation energy which is nonzero solely because of overlap of the ion wavefunctions. The results presented for NaCl, MgO and the fluorides of Li, Na, Ag and Pb show that these modifications overcome the deficiencies of previous calculations. Ab initio predictions of the closest cation-cation and anion-anion short-range interactions, which are not available from semi-empirical fits to experimental data, are presented. The non-point coulombic interactions between pairs of anions, derived by adding the dispersive attractions to the short-range interactions, are compared with previous semi-empirical and approximate ab initio results. The uncorrelated short-range inter-ionic potentials computed exactly are compared with those predicted from electron-gas theory. The use of the electron-gas approximation to describe any of these potentials degrades the quality of the predicted crystal properties.