title: Reaction path analysis of the "tunable" photoisomerization selectivity of free and locked retinal chromophores.
abstract: Multiconfigurational second-order perturbation theory computations and reaction path mapping for the retinal protonated Schiff base models all-trans-nona-2,4,6,8-tetraeniminium and 2-cis-nona-2,4,6,8-tetraeniminium cation demonstrate that, in isolated conditions, retinal chromophores exhibit at least three competing excited-state double bond isomerization paths. These paths are associated with the photoisomerization of the double bonds in positions 9, 11, and 13, respectively, and are controlled by barriers that favor the position 11. The computations provide a basis for the understanding of the observed excited-state lifetime in both naturally occurring and synthetic chromophores in solution and, tentatively, in the protein environment. In particular, we provide a rationalization of the excited-state lifetimes observed for a group of locked retinal chromophores which suggests that photoisomerization in bacteriorhodopsin is the result of simultaneous specific "catalysis" (all-trans --> 13-cis path) accompanied by specific "inhibition" (all-trans --> 11-cis path). The nature of the S(1) --> S(0) decay channel associated with the three paths has also been investigated at the CASSCF level of theory. It is shown that the energy surfaces in the vicinity of the conical intersection for the photoisomerization about the central double bond of retinal (position 11) and the two corresponding lateral double bonds (positions 9 and 13) are structurally different.
authors.affiliation: Dipartimento di Chimica, Università di Siena, via Aldo Moro, Siena, I-53100 Italy.
authors.forename: Luca
authors.initials: L
authors.lastname: De Vico
authors.forename: Christopher S
authors.initials: CS
authors.lastname: Page
authors.forename: Marco
authors.initials: M
authors.lastname: Garavelli
authors.forename: Fernando
authors.initials: F
authors.lastname: Bernardi
authors.forename: Riccardo
authors.initials: R
authors.lastname: Basosi
authors.forename: Massimo
authors.initials: M
authors.lastname: Olivucci
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D018716:Molecular Mimicry; D010777:Photochemistry; D012172:Retinaldehyde / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000475:Alkenes; D007097:Imines; C456417:nona-2,4,6,8-tetraenimine; D012172:Retinaldehyde