Theoretical investigations of the nature of intramolecular interactions

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Abstract
The description of intramolecular interactions by a single-determinant wave function of non-orthogonal, strictly local, molecular orbitals (NOLMOs) is improved by the admission of electron charge transfer into anti-bonding orbitals. An energy decomposition scheme in terms of quasiclassical (overlap independent), interference (overlap dependent) and charge transfer components is outlined. The formalism is applied to the study of the barrier to internal rotation in ethane. It is found that vicinal CH-CH′ interactions and non-additivity effects on geminal CH-CH interactions constitute the two major contributions to the barrier.

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