Theoretical analysis of structural stability of TM5 Si 3 transition metal silicides

Abstract

A combination of electronic-structure calculations from density-functional theory (DFT) through a tight-binding (TB) model to analytic bond-order potentials (BOPs) has been used to investigate the structural trend of the TM5 Si3 compounds across the early transition metals (TM). First of all, the formation energies of TM5 Si3, whose ground states adopt the competing D 88, D 8l, or D 8 m structure types, have been calculated by using DFT (TM is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W). In agreement with experiments the DFT results predict the observed D 88 →D 8m structural trend across the 3d series and the D 88 →D 8l →D 8m trend across the 4d and 5d series. A p-d canonical TB model is then shown to reproduce these trends, thereby providing a valid basis for the application of BOP theory. By performing a moment analysis within the BOP formalism, we conclude that up to the fifth moment of the density of states is required to explain the structural trend across the 3d series whereas up to the ninth moment is required for the 4d and 5d series.