Dissociation Curves and Binding Energies of Diatomic Transition Metal Carbides from Density Functional Theory

    Authors

    S. Goel;A. E. Masunov

    Comments

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    Abbreviated Journal Title

    Int. J. Quantum Chem.

    Keywords

    3d-transition metals; relativistic correction; potential energy curve; hybrid exchange-correlation functional; unrestricted Kohn-Sham; broken-symmetry DFT; AB-INITIO INVESTIGATIONS; ELECTRONIC-STRUCTURE; NONCOVALENT; INTERACTIONS; THERMOCHEMICAL KINETICS; TITANIUM CARBIDE; EXACT-EXCHANGE; STATES; ATOMS; MOLECULE; CRC; Chemistry, Physical; Mathematics, Interdisciplinary Applications; Physics, Atomic, Molecular & Chemical

    Abstract

    The 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 (tau-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. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111: 4276-4287, 2011

    Journal Title

    International Journal of Quantum Chemistry

    Volume

    111

    Issue/Number

    15

    Publication Date

    1-1-2011

    Document Type

    Article

    Language

    English

    First Page

    4276

    Last Page

    4287

    WOS Identifier

    WOS:000295373500026

    ISSN

    0020-7608

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