Dissociation curves and binding energies of diatomic transition metal carbides from density functional theory

Abstract

AbstractThe computational description of the catalytic processes on the surface of transition metals (TMs) requires methods capable of accurate prediction of the bond forming and breaking between the atoms of metal and other elements. In our previous report [Goel and Masunov, J Chem Phys, 129, 214302, 2008], we studied TM hydrides and found that Boese–Martin functional for kinetics (BMK) combined with broken symmetry approach described dissociation process more accurately than multireference wavefunction theory (WFT) methods and some other functionals. Here, we investigate the binding energy, geometry, electronic structure, and potential energy curves for diatomic TM carbides using several exchange‐correlation functionals. The functionals that include explicit dependence on the kinetic energy density (τ‐functionals) are considered, among others. We have found M05‐2x performance to be the best, followed by BMK, when compared with experimental and high level WFT energetics. This agreement deteriorates quickly for other functionals when the fraction of the Hartree–Fock exchange is decreased. Scalar relativistic corrections yield mixed results for bond lengths and bond energies. The natural bond orbital analysis provides useful insight in description of stable spin state over others in these diatomics. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011