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The Application of Nonlocal and Self-Consistent Density Functional Theory to Molecular Problems

  • Chapter
Density Functional Theory of Molecules, Clusters, and Solids

Part of the book series: Understanding Chemical Reactivity ((UCRE,volume 12))

Abstract

A self consistent nonlocal density functional method (NL-SCF) based on the gradient corrected exchange term by Becke [Phys. Rev. A38, 3098(1988)] and a gradient corrected correlation term by Perdew [Phys. Rev. B33, 8822(1986)] has been implemented into the LCAO-HFS program by Baerends et al. [Chem. Phys. 2, 41(1973)]. An expression for the variational potential corresponding to Becke’s gradient correction has been derived. A detailed analysis is given of the change in density, 5p, induced by the gradient corrections. It is shown that δp is two orders of magnitude smaller than the deformation density Δρ = ρmolecule -ρatom. The dipole moments calculated by NL-SCF differ as a consequence only modestly from dipole moments obtained by the Local Density Approximation (LDA) in which the gradient corrections are absent. The importance of self-consistency for calculations on bond distances, bond energies and vibrational frequencies are assessed by comparing results from NL-SCF calculations with data obtained by a perturbative approach (NL-P) in which densities obtained from LDA calculation were used in the evaluation of the gradient corrections. It is further shown that results from calculations on metal-ligand bond distances and bond energies are improved considerably by nonlocal corrections.

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  1. Department of Chemistry, University of Calgary, Calgary, Alberta, Canada, T2N 1N4

    Liangyou Fan & Tom Ziegler

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  1. Liangyou Fan
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  2. Tom Ziegler
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  1. Department of Chemistry, Northwestern University, Evanston, Illinois, USA

    D. E. Ellis

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© 1996 Colin WIllmer and Mark Fricker

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Fan, L., Ziegler, T. (1996). The Application of Nonlocal and Self-Consistent Density Functional Theory to Molecular Problems. In: Ellis, D.E. (eds) Density Functional Theory of Molecules, Clusters, and Solids. Understanding Chemical Reactivity, vol 12. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0487-6_3

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  • DOI: https://doi.org/10.1007/978-94-011-0487-6_3

  • Publisher Name: Springer, Dordrecht

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