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.

Electronic excitation energies of molecules in solution: State specific and linear response methods for nonequilibrium continuum solvation models / Cammi, Roberto; S., Corni; B., Mennucci; J., Tomasi. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 122:(2005), pp. 104513-1-104513-12. [10.1063/1.1867373]

Electronic excitation energies of molecules in solution: State specific and linear response methods for nonequilibrium continuum solvation models

CAMMI, Roberto;
2005-01-01

Abstract

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.
2005
Electronic excitation energies of molecules in solution: State specific and linear response methods for nonequilibrium continuum solvation models / Cammi, Roberto; S., Corni; B., Mennucci; J., Tomasi. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 122:(2005), pp. 104513-1-104513-12. [10.1063/1.1867373]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/1444365
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