Theoretical Electronic Spectrum of the Allyl System

Abstract

Properties of π electrons in allyl anion, cation, and radical are calculated by including interaction between antisymmetrized products of molecular orbital functions. Detailed results in the form of energies and orbital composition of π-electron state functions for the anion as well as transition intensities and energies for all three molecules, including and excluding configurational interaction, are presented. The extent to which a valence bond type wave function resembles an obtained state function is investigated by the computation of overlaps between the two functions. The overlaps and energies of various valence bond type functions are presented and suggest a relatively greater applicability of the valence bond approach in the case of the neutral radical compared to that of the ions.