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On the Accuracy of the Algebraic Approximation in Molecular Electronic Structure Studies: VII. Matrix Valence Bond Calculations for the Hydrogen Molecule Ground State

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Quantum Systems in Chemistry and Physics. Trends in Methods and Applications

Part of the book series: Topics in Molecular Organization and Engineering ((MOOE,volume 16))

Abstract

The accuracy of generalized valence bond calculations made within the algebraic approximation (that is by making finite basis set expansions) is investigated by using systematic sequences of distributed even-tempered Gaussian basis sets for the ground state of the hydrogen molecule. In contrast to the matrix Hartree—Fock model, the valence bond model approach afford a qualitatively correct description of molecular dissociation processes and provides a useful reference with respect to which dynamic electron correlation effects can be described. A basis set is developed which supports an accuracy approaching the sub-μhartree level in energy calculations using the matrix valence bond and matrix Hartree—Fock approaches. A comparison is made with the results of second-order many-body perturbation theory calculations. An interpretation of the utility of bond-centred basis functions is provided in terms of generalized valence bond theory.

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Author information

Authors and Affiliations

  1. Supercomputer Computations Research Institute, Florida State University, Tallahassee, Florida, USA

    D. Moncrieff

  2. Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX11 0QX, UK

    S. Wilson

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  1. D. Moncrieff
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  2. S. Wilson
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Roy McWeeny Jean Maruani Yves G. Smeyers Stephen Wilson

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© 1997 Springer Science+Business Media Dordrecht

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Moncrieff, D., Wilson, S. (1997). On the Accuracy of the Algebraic Approximation in Molecular Electronic Structure Studies: VII. Matrix Valence Bond Calculations for the Hydrogen Molecule Ground State. In: McWeeny, R., Maruani, J., Smeyers, Y.G., Wilson, S. (eds) Quantum Systems in Chemistry and Physics. Trends in Methods and Applications. Topics in Molecular Organization and Engineering, vol 16. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4894-8_18

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  • DOI: https://doi.org/10.1007/978-94-011-4894-8_18

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6052-3

  • Online ISBN: 978-94-011-4894-8

  • eBook Packages: Springer Book Archive

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