Computational evidence in favor of a two-state, two-mode model of the retinal chromophore photoisomerization

In this paper we use ab initio multiconfigurational second-order perturbation theory to establish the intrinsic photoisomerization path model of retinal chromophores. This is accomplished by computing the ground state (S(0)) and the first two singlet excited-state (S(1), S(2)) energies along the rigorously determined photoisomerization coordinate of the rhodopsin chromophore model 4-cis-γ-methylnona-2,4,6,8-tetraeniminium cation and the bacteriorhodopsin chromophore model all-trans-hepta-2,4,6-trieniminium cation in isolated conditions. The computed S(2) and S(1) energy profiles do not show any avoided crossing feature along the S(1) reaction path and maintain an energy gap >20 kcal⋅mol(−1). In addition, the analysis of the charge distribution shows that there is no qualitative change in the S(2) and S(1) electronic structure along the path. Thus, the S(1) state maintains a prevalent ionic (hole–pair) character whereas the S(2) state maintains a covalent (dot–dot) character. These results, together with the analysis of the S(1) reaction coordinate, support a two-state, two-mode model of the photoisomerization that constitutes a substantial revision of the previously proposed models.