Electrostatic interactions as a factor in the determination of the HOMO in the liquid state

Abstract

An ellipsoidal cavity model has been used to study the energy changes in occupied molecular orbitals induced by solute–solvent electrostatic interactions. Some benzene derivatives have been selected as solutes. Calculations have been carried out at the CNDO and abinitio STO-4G levels. Important variations in the molecular orbital sequence, involving a change in the HOMO nature, have been observed. A perturbation analysis is employed to understand the orbital evolution from gas phase to solution.