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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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
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