title: Toward Understanding the Photochemistry of Photoactive Yellow Protein: A CASPT2/CASSCF and Quantum Theory of Atoms in Molecules Combined Study of a Model Chromophore in Vacuo.
abstract: Photochemical processes that take place in biological molecules have become an increasingly important research topic for both experimentalists and theoreticians. In this work, we report the reaction mechanism of a model of the photoactive yellow protein (PYP) chromophore in vacuo. The results obtained here, using a strategy based on the simultaneous use of the minimum energy path concept and the quantum theory of atoms in molecules applied to this excited state process, suggest a possible way in which the protein could increase the efficiency of the reaction. The role played by other electronic states of the same and different spin multiplicities in the reaction process is also analyzed, with special emphasis on that played by the lowest-lying triplet state. The possibility of a more complex than expected reaction mechanism is finally discussed, with some suggestions on the possible roles of the protein.
authors.affiliation: Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, Apdo. 22085, ES-46071, Valencia, Spain, Departamento de Química-Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006, Oviedo, Spain, Departamento de Química-Física y Analítica, Universidad Jaume I, 224, 12071, Castellón, Spain.
authors.forename: P B
authors.initials: PB
authors.lastname: Coto
authors.affiliation: Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, Apdo. 22085, ES-46071, Valencia, Spain, Departamento de Química-Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006, Oviedo, Spain, Departamento de Química-Física y Analítica, Universidad Jaume I, 224, 12071, Castellón, Spain.
authors.forename: D
authors.initials: D
authors.lastname: Roca-Sanjuán
authors.affiliation: Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, Apdo. 22085, ES-46071, Valencia, Spain, Departamento de Química-Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006, Oviedo, Spain, Departamento de Química-Física y Analítica, Universidad Jaume I, 224, 12071, Castellón, Spain.
authors.forename: L
authors.initials: L
authors.lastname: Serrano-Andrés
authors.affiliation: Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, Apdo. 22085, ES-46071, Valencia, Spain, Departamento de Química-Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006, Oviedo, Spain, Departamento de Química-Física y Analítica, Universidad Jaume I, 224, 12071, Castellón, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Martín-Pendás
authors.affiliation: Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, Apdo. 22085, ES-46071, Valencia, Spain, Departamento de Química-Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006, Oviedo, Spain, Departamento de Química-Física y Analítica, Universidad Jaume I, 224, 12071, Castellón, Spain.
authors.forename: S
authors.initials: S
authors.lastname: Martí
authors.affiliation: Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, Apdo. 22085, ES-46071, Valencia, Spain, Departamento de Química-Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006, Oviedo, Spain, Departamento de Química-Física y Analítica, Universidad Jaume I, 224, 12071, Castellón, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Andrés