Effects of dispersion corrections on the theoretical description of bulk metals

Abstract

The addition of a London dispersion correction to standard Kohn-Sham density-functional theory is essential for an accurate description of noncovalent interactions. While several dispersion-corrected density functionals (DC-DFs) have shown excellent performance for hard solids at ambient conditions, their transferability to metallic systems at ambient conditions or under isotropic compression has not been systematically examined. In this study, we assess the ability of selected DC-DFs to describe the equations of state (EOSs) of selected elemental metals and intermetallic compounds up to several gigapascals of pressure. EOS-derived properties, such as the unit-cell volume, the bulk modulus, and its pressure derivative, were then evaluated with and without thermal effects and the results compared with experimental reference data. We also assess the ability of the DC-DFs to predict the phase-transition pressures for a set of intermetallic compounds. The results of this study establish that London dispersion physics, and even dispersion contributions from the core electrons, is important in the description of bulk metals.