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Comparison of the Hartree-Fock, Møller-Plesset, and Hartree-Fock-Slater method with respect to electrostatic properties of small molecules

Effects of electron correlation

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Summary

The results of various quantum chemical calculations, the Hartree-Fock (HF) method, the Møller-Plesset perturbation theory (MP2), and the Hartree-Fock-Slater (HFS) method are compared. Atomic charges, dipole moments, topological properties of the electron density distribution and polarizabilities, and first hyperpolarizabilities are calculated. Atomic charges obtained with the HFS method are found to be very close to those calculated with the MP2 method, from which we conclude that the HFS method describes to some extent electron correlation effects. Performing an MP2 calculation after an HF calculation improves the molecular dipole moments considerably, yielding values close to the experimental ones. HFS calculations are computationally less demanding than MP2 and yield comparable results for the electron density distributions, dipole moments and polarizabilities.

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Authors and Affiliations

  1. Chemical Physics Laboratory, University of Twente, PO Box 217, NL-7500 AE, Enschede, The Netherlands

    Guus J. M. Velders & Dirk Feil

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  1. Guus J. M. Velders
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  2. Dirk Feil
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Velders, G.J.M., Feil, D. Comparison of the Hartree-Fock, Møller-Plesset, and Hartree-Fock-Slater method with respect to electrostatic properties of small molecules. Theoret. Chim. Acta 86, 391–416 (1993). https://doi.org/10.1007/BF01122431

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  • DOI: https://doi.org/10.1007/BF01122431

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