Excited state electronic polarization and reappraisal of the n <- pi* emission of acetone in water

Electronic polarization of the acetone molecule in the excited n -> pi* state is considered and its influence on the solvent shift in the emission spectrum is analyzed. Using an iterative procedure the electronic polarizations of both the ground and the excited states are included and compared with previous results obtained with Car-Parrinello dynamics. Analysis of the emission transition obtained using CIS(D)/aug-cc-pVDZ on statistically uncorrelated solute-solvent structures, composed of acetone and twelve explicit water molecules embedded in the electrostatic field of remaining 263 water molecules, corroborates that the solvent effect is mild, calculated here between 80 and 380 cm (1). (c) 2010 Published by Elsevier B.V.

INCT-GFCx

INCT-GFCx

NbioNet

NbioNet

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

CNPq

CAPES

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

FAPESP (Brazil)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)