Theoretical investigations of the nature of intramolecular interactions

Abstract

The use of non-orthogonal localized molecular orbitals (NOLMOs) for the construction of the one-electron density of closed shell molecules is investigated. Special attention is focused on the transferability properties of NOLMOs. Standard NOLMOs, optimized in small molecules with a split valence basis set, produce reasonable optimized geometries in these small molecules and are able to predict geometry changes in going from mono- to difluoromethane. A simple pictorial model is presented. It is concluded that NOLMOs possess a high degree of transferability, which can be used for the construction of a wavefunction for larger molecules.