Trends in the chemical properties of early transition metal carbide surfaces: A density functional study

In this paper we present density functional theory (DFT) investigations of the physical, chemical and electronic structure properties of several close-packed surfaces of early transition metal carbides, including β-Mo2C(0 0 0 1), and the (1 1 1) surfaces of TiC, VC, NbC, and TaC. The results are in excellent agreement with experimental values of lattice constants and bulk moduli. The adsorption of atomic hydrogen is used as a probe to compare the chemical properties of various carbide surfaces. Hydrogen adsorbs more strongly to the metal-terminated carbide surfaces than to the corresponding closest-packed pure metal surfaces, due to the tensile strain induced in the carbide surfaces upon incorporation of carbon into the lattice. Hydrogen atoms were found to adsorb more weakly on carbide surfaces than on the corresponding closest-packed pure metal surfaces only when there were surface carbon atoms present, and in some cases very stable C–H species were formed. The DFT results indicated that the hydrogen adsorption energy could be correlated to the d-band center of the carbide surfaces, although the correlation was not as good as our previous studies on bimetallic surfaces.