Simultaneous Solvent and Counterion Effects on the Absorption Properties of a Model of the XXXX Chromophore.

@entity13479 @entity1044 @entity8695 @entity1042 @entity3364 @entity601
The ASEP/ @entity601 (averaged solvent electrostatic potential from molecular dynamics) method was employed in studying the environment effects (solvent and counterion) on the absorption spectrum of a model of the 11-cis-retinal protonated @entity3364 . Experimental studies of the absorption spectra of the @entity8695 chromophore show anomalously large solvent shifts in apolar solvents. In order to clarify their origin, we study the role of the counterion and of the solute-solvent interactions. We compare the absorption spectra in the gas phase, @entity13479 , @entity1044 , and @entity1042 . The counterion effect was described from both a classical and quantum point of view. In the latter case, the contribution of the chromophore-counterion charge transfer to the solvent shift could be analyzed. To the best of our knowledge, this is the first time that counterion and solvent effects on the absorption properties of the 11-cis-retinal chromophore have been simultaneously examined. We conclude that the counterion-solute ionic pair in the gas phase is not a good model to represent the solvent shift in nonpolar solvents, as it does not account for the effect that the thermal agitation of the solvent has on the geometry of the ionic pair. In contrast to nonpolar solvents, the experimental solvent shift values in @entity1042 can be exclusively explained by the polarity of the medium. In @entity1044 , the presence of the counterion does not modify the solvent shift of the first absorption band, but it affects the position of the second excited state. In the three solvents considered, the first two excited states become almost degenerate.
