title: Optomechanical Control of Quantum Yield in Trans-Cis Ultrafast Photoisomerization of a Retinal Chromophore Model.
abstract: The quantum yield of a photochemical reaction is one of the most fundamental quantities in photochemistry, as it measures the efficiency of the transduction of light energy into chemical energy. Nature has evolved photoreceptors in which the reactivity of a chromophore is enhanced by its molecular environment to achieve high quantum yields. The retinal chromophore sterically constrained inside rhodopsin proteins represents an outstanding example of such a control. In a more general framework, mechanical forces acting on a molecular system can strongly modify its reactivity. Herein, we show that the exertion of tensile forces on a simplified retinal chromophore model provokes a substantial and regular increase in the trans-to-cis photoisomerization quantum yield in a counterintuitive way, as these extension forces facilitate the formation of the more compressed cis photoisomer. A rationale for the mechanochemical effect on this photoisomerization mechanism is also proposed.
authors.affiliation: Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Ctra. A2 Km 33,6, 28871, Alcalá de Henares, Spain.|Department of Biotechnology, Chemistry and Pharmacy, University of Siena, via A. Moro 2, 53100, Siena, Italy.
authors.forename: Alessio
authors.initials: A
authors.lastname: Valentini
authors.affiliation: Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Ctra. A2 Km 33,6, 28871, Alcalá de Henares, Spain.
authors.forename: Daniel
authors.initials: D
authors.lastname: Rivero
authors.affiliation: Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Ctra. A2 Km 33,6, 28871, Alcalá de Henares, Spain.
authors.forename: Felipe
authors.initials: F
authors.lastname: Zapata
authors.affiliation: Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Ctra. A2 Km 33,6, 28871, Alcalá de Henares, Spain.|Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), University of La Rioja, Madre de Dios, 53, 26006, Logroño, Spain.
authors.forename: Cristina
authors.identifier: 0000-0002-7577-8242
authors.initials: C
authors.lastname: García-Iriepa
authors.affiliation: Theory-Modeling-Simulation SRSMC, Université de Lorraine-Nancy, Vandoeuvre-lès-Nancy, Nancy, France.|Theory-Modeling-Simulation SRSMC, CNRS, SRSMC Boulevard des Aiguillettes, Vandoeuvre-lès-Nancy, France.
authors.forename: Marco
authors.identifier: 0000-0001-7158-7994
authors.initials: M
authors.lastname: Marazzi
authors.affiliation: Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Ctra. A2 Km 33,6, 28871, Alcalá de Henares, Spain.
authors.forename: Raúl
authors.identifier: 0000-0002-0907-006X
authors.initials: R
authors.lastname: Palmeiro
authors.affiliation: Department of Chemistry-Ångström, Uppsala Center for Computational Chemistry-UC3, Uppsala University, Box 518, 75120, Uppsala, Sweden.
authors.forename: Ignacio
authors.identifier: 0000-0002-0684-7689
authors.initials: I
authors.lastname: Fdez Galván
authors.affiliation: Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), University of La Rioja, Madre de Dios, 53, 26006, Logroño, Spain.
authors.forename: Diego
authors.identifier: 0000-0003-2772-6453
authors.initials: D
authors.lastname: Sampedro
authors.affiliation: Department of Biotechnology, Chemistry and Pharmacy, University of Siena, via A. Moro 2, 53100, Siena, Italy.|Department of Chemistry, Bowling Green State University, Bowling Green, OH, 43403, USA.|USIAS and Institut de Physique et Chimie des Matériaux de Strasbourg, Université de Strasbourg-CNRS, 67034, Strasbourg, France.
authors.forename: Massimo
authors.identifier: 0000-0002-8247-209X
authors.initials: M
authors.lastname: Olivucci
authors.affiliation: Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Ctra. A2 Km 33,6, 28871, Alcalá de Henares, Spain.
authors.forename: Luis Manuel
authors.identifier: 0000-0003-1036-7108
authors.initials: LM
authors.lastname: Frutos
mesh_terms: D008956:Models, Chemical; D015394:Molecular Structure; D055668:Photochemical Processes; D011789:Quantum Theory; D012172:Retinaldehyde / Q000737:chemistry*; D012243:Rhodopsin / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D012243:Rhodopsin; D012172:Retinaldehyde
keywords: mechanochemistry; photoisomerization; quantum yield control; retinal models; semiclassical dynamics