Localization and delocalization: Distinction between through space and through bond interactions

Abstract
We propose a special perturbation formalism based on the local Brillouintheorem to study the effects causing delocalization (’’tails’’) of bond orbitals. Assuming a given one‐electron Hamiltonian, an explicit recursion relation is derived for the tails to any order. It permits to distinguish between the ’’through space’’ effects caused by the direct interaction of bonds, and the ’’through bond’’ ones which appear in higher orders. Application of the results to SCF‐type theories indicates that only through space interactions like vicinal ones are orientation sensitive.

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