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

TL;DR

This study uses density-functional theory to analyze electronic structures and bonding trends in early transition-metal carbides, revealing the significance of C--C bonds and providing detailed insights into their covalent and ionic characteristics.

Contribution

It offers a systematic DFT-based analysis of bonding and electronic trends in TMCs, highlighting the role of C--C bonds often overlooked in previous studies.

Findings

Confirmation of TM--C and TM--TM bonds

Identification of direct C--C bonds in all TMCs

Analysis of covalency and ionicity trends

Abstract

A detailed and systematic density-functional theory (DFT) study of a series of early transition-metal carbides (TMC's) 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 TMC's. 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 wave functions to gain 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 TMC's, which are frequently neglected but have been recently identified in some cases [Solid State Commun. 121, 411 (2002); Phys. Rev. B 75, 235438 (2007)]. New information on the spatial extent of the bonds, their \textit{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.