The ring opening of cyclopropylidene to allene and the isomerization of allene:ab initio interpretation of the electronic rearrangements in terms of quasi-atomic orbitals

Abstract

A full optimized reaction space (FORS) remains invariant under arbitrary orthogonal transformations among its configuration-generating molecular orbitals. Localization of the latter for a FORS wavefunction yields molecular orbitals withquasi-atomic character which can be interpreted asmolecule-adapted minimal-basis-set atomic orbitals. In terms of these quasi-atomic FORS MOs, the configuration mixing in the FORS wavefunction, the representation of the density matrix, and the expansions of the natural orbitals provide information about the interactions that are responsible for the molecular energy changes. A basis-set-independent population analysis can be formulated which accomplishes the objectives of Mulliken's population analysis without the drawbacks stemming from the basis-set dependence of the latter. Through application of these procedures, explanations can be found for various features of the potential energy surface governing the ring opening of cyclopropylidene and the isomerization of allene.