Density-functional study of bulk and surface properties of titanium nitride using different exchange-correlation functionals

Abstract

The adsorption and diffusion of hydrogen on the (100) surface of titanium nitride was studied using density-functional theory (DFT) and the generalized gradient approximation (GGA) for the exchange and correlation energy. The adsorption site was found to be on top of the titanium atom with the chemisorption energy of -2.88 eV. The diffusion barrier was determined as 0.73 eV along the path connecting the neighboring titanium atoms. The surface energies and surface relaxations of the three most important surfaces of TiN were studied. The surface energies have the following order: ${S}_{100}<{S}_{110}<{S}_{111}.$ Three different GGA functionals, the Perdew-Wang 1991 (PW91), the Perdew-Burke-Ernzerhof (PBE), and the revised PBE (RPBE) functionals, were tested on crystals, small molecules and TiN surfaces. The RPBE functional when applied to the surface studies of TiN was found to produce slightly lower values of surface energies and of hydrogen adsorption energies than the PW91 functional.