Trends in bulk electron-structural features of rocksalt early transition-metal carbides

Artikel i vetenskaplig tidskrift, 2010

A detailed and systematic density-functional theory (DFT) study of a series of early transition-metal carbides (TMCs) in the NaCl structure is presented. The focus is on the trends in the electronic structure and nature of bonding, which are essential for the understanding of the reactivity of TMCs. The employed approach is based on a thorough complementary analysis of the electron density differences, the density of states (DOS), the band structure and the real-space wavefunctions to gain an insight into the bonding of this class of materials and get a more detailed picture of it than previously achieved, as the trend study allows for a systematic identification of the bond character along the different bands. Our approach confirms the presence of both the well-known TM-C and TM-TM bonds and, more importantly, it shows the existence and significance of direct C-C bonds in all investigated TMCs, which are frequently neglected but have been identified in some cases (Zhang et al 2002 Solid State Commun. 121 411; Ruberto et al 2007 Phys. Rev. B 75 235438). New information on the spatial extent of the bonds, their k-space location within the band structure and their importance for the bulk cohesion is provided. Trends in covalency and ionicity are presented. The resulting electron-structural trends are analyzed and discussed within a two-level model.