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p-Benzoquinone in aqueous solution: Stark shifts in spectra, asymmetry in solvent structure
Authors:Ohrn Anders  Aquilante Francesco
Affiliation:Department of Theoretical Chemistry, Chemical Centre, P.O.B 124, S-221 00 Lund, Sweden. anders.ohrn@teokem.lu.se
Abstract:Results from a simulation of p-benzoquinone (PBQ) in water is presented. An explicit solvent representation is used together with a multiconfigurational ab initio quantum chemical method. The electronic n --> pi* transitions are studied in aqueous solution and the two such transitions are both blue-shifted but to different degree. Both non-equilibrium and many-body effects are found to have decisive influence on the solvation: despite stronger hydrogen bonding between solute and solvent in an excited state than in the ground state, there is a blue-shift, and the solvent structure around the non-polar PBQ is asymmetric, which is argued to come from special many-body effects. The unusual result of strengthened hydrogen bonds in the excited state that follows from an excitation of a non-bonding electron on a proton acceptor, is explained by the near-linear Stark shift that is present in the transition.
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