title: Excited-state singlet manifold and oscillatory features of a nonatetraeniminium retinal chromophore model.
abstract: In this paper we use ab initio multireference Møller-Plesset second-order perturbation theory computations to map the first five singlet states (S(0), S(1), S(2), S(3), and S(4)) along the initial part of the photoisomerization coordinate for the isolated rhodopsin chromophore model 4-cis-gamma-methylnona-2,4,6,8-tetraeniminium cation. We show that this information not only provides an explanation for the spectral features associated to the chromophore in solution but also, subject to a tentative hypothesis on the effect of the protein cavity, may be employed to explain/assign the ultrafast near-IR excited-state absorption, stimulated emission, and transient excited-state absorption bands observed in rhodopsin proteins (e.g. rhodopsin and bacteriorhodopsin). We also show that the results of vibrational frequency computations reveal a general structure for the first (S(1)) excited-state energy surface of PSBs that is consistent with the existence of the coherent oscillatory motions observed both in solution and in bacteriorhodopsin.
authors.affiliation: Dipartimento di Chimica, Università di Siena, via Aldo Moro, Siena, I-53100 Italy.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Cembran
authors.forename: Fernando
authors.initials: F
authors.lastname: Bernardi
authors.forename: Massimo
authors.initials: M
authors.lastname: Olivucci
authors.forename: Marco
authors.initials: M
authors.lastname: Garavelli
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D012172:Retinaldehyde / Q000737:chemistry*; D012243:Rhodopsin / Q000737:chemistry; D012545:Schiff Bases / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013816:Thermodynamics
chemical_list: C479558:4-methylnona-2,4,6,8-tetraenimine; D007097:Imines; D012545:Schiff Bases; D012243:Rhodopsin; D012172:Retinaldehyde