Macroscopic solvent polarization-induced reorganization of the electron density in different excited states: a study on formaldehyde molecule by a multiconfiguration self-consistent reaction-field method

Abstract

A detailed study of the type and extent of electronic reorganization created by macroscopic solvation of a prototypical carbonyl solute is carried out within the framework of the semiempirical multiconfiguration self-consistent reaction-field model. The solvation causes additional polarization of the electronic charge density within the carbonyl group. Orbitalwise breakup of the electron densities on the key atoms throws light on such features as the polarity dependence of inversion barriers and out-of-plane bending. Macroscopic solvation is shown to cause a reverse π-polarization within the carbonyl group, affecting barrier heights on the inversion path.