We present a formal comparison between the two different approaches to the calculation of electronic excitation energies of molecules in solution within the continuum solvation model framework, taking also into account nonequilibrium effects. These two approaches, one based on the explicit evaluation of the excited state wave function of the solute and the other based on the linear response theory, are here proven to give formally different expressions for the excitation energies even when exact eigenstates are considered. Calculations performed for some illustrative examples show that this formal difference has sensible effects on absolute solvatochromic shifts (i.e., with respect to gas phase) while it has small effects on relative (i.e., nonpolar to polar solvent) solvatochromic shifts.
|Autori:||R. CAMMI; S. CORNI; MENNUCCI B; J. TOMASI|
|Titolo:||Electronic excitation energies of molecules in solution: State specific and linear response methods for non-equilibrium continuum solvation models|
|Anno del prodotto:||2005|
|Digital Object Identifier (DOI):||10.1063/1.1867373|
|Appare nelle tipologie:||1.1 Articolo in rivista|