Reaction field spectral shifts with semiempirical molecular orbital theory

Abstract

A macroscopic solution polarization free-energy functional is combined with semiempirical molecular orbital theory to study shifts of electronic absorption energies for several molecules in solution. The present method requires calculation of the induced electrostatic potential on the van der Waals surface and this calculation is implemented in a new way. The combined method is tested by calculating absorption energy shifts for several molecules of standard interest. We find the physically reasonable result that there is a correlation between the absorption energy shift and the magnitude of the dipole moments of the initial and final states involved in the absorption transition. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 64: 143–155, 1997