Conformational energetics and excited state level ordering in 11-cis retinal

Semiempirical molecular orbital theory and semiclassical solvent effect theory are used to analyze the conformational and electronic properties of the 12-s-cis and 12-s-trans conformers of 11-cis retinal. The goal is to examine the influence of solvent environment on the equilibrium geometries of these conformers as well as to provide a perspective on the electronic transitions that contribute to the four band systems that are observed in the 200-500 nm region of the optical spectrum. We conclude that the 12-s-cis isomer is more stable in vacuum, but that the 12-s-trans conformer is preferentially stabilized in both polar and nonpolar solvent environment due to dispersive as well as electrostatic interactions. This observation is in substantial agreement with previous literature results. In contrast, our analysis of the excited state manifold indicates that the spectral features observed in the absorption spectrum are associated with a complex set of overlapping transitions. A total of 18 pi*<--pi transitions contribute to the four bands, and in some cases, conformation changes the relative contribution of the individual transitions that define the overall band shape. This study provides the first definitive assignments for all four band systems.