Localization and delocalization. II. Role of overlap in interbond interactions

A special perturbational theory for intramolecular electron delocalization is presented taking into account the nonorthogonality of basis orbitals. First, a biorthogonal formulation is proposed in which no series expansion is made for the overlaps. Then a partition of the overlap matrix S is also introduced which permits to incorporate the overlap effects into the perturbational expansion. The latter approach allows to discuss the role of overlap in ‘‘through space’’ and ‘‘through bond’’ interactions causing electron delocalization. Both formalisms are illustrated by some numerical examples.

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