Bond deformation paths and electronic instabilities of ultraincompressible transition metal diborides: Case study of OsB2 and IrB2

Abstract

The energetically most stable orthorhombic structure of OsB2 and IrB2 is dynamically stable for OsB2 but unstable for IrB2. Both diborides have substantially lower shear strength in their easy slip systems than their metal counterparts. This is attributed to an easy sliding facilitated by out-of-plane weakening of metallic Os-Os bonds in OsB2 and by an in-plane bond splitting instability in IrB2. A much higher shear resistance of Os-B and B-B bonds than Os-Os ones is found, suggesting that the strengthened Os-B and B-B bonds are responsible for hardness enhancement in OsB2. In contrast, an in-plane electronic instability in IrB2 limits its strength. The electronic structure of deformed diborides suggests that the electronic instabilities of 5d orbitals are their origin of different bond deformation paths. Neither IrB2 nor OsB2 can be intrinsically superhard.