Abstract
In an orthogonalized basis, the diagonal element Fμμ of the Fock operator, for a number of semiempirical MO LCAO methods, can be represented by a trinomial which is quadratic with respect to the Mulliken charge. The coefficients differ for different methods, depending on the manner in which the interelectronic interaction is taken into account. From a study, in general form, of the influence of change in the coefficients of the trinomial Fμμ on the bond order matrix, an explanation has been given for certain familiar calculation results: the equalization of the π-charges on going from the Hückel method to the more advanced techniques, and the decrease in the covalent character of metal-ligand bonds when allowance is made for the interelectronic interaction in the calculations for complexes.
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In conclusion, we wish to thank V. D. Sutula and L. I. Chernyavskii for much valuable discussion.
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Zeif, A.P. Comparison of various semiempirical MO LCAO methods. Theor Exp Chem 5, 192–196 (1969). https://doi.org/10.1007/BF01109661
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DOI: https://doi.org/10.1007/BF01109661