Title

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

Authors

Authors

S. Goel;A. E. Masunov

Comments

Authors: contact us about adding a copy of your work at STARS@ucf.edu

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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