Photochemistry and Photophysics at Extended Seams of Conical Intersection
The role of extended seams of conical intersection in excited-state mechanisms is reviewed. Seams are crossings of the potential energy surface in many dimensions where the decay from the excited to the ground state can occur, and the extended seam is composed of different segments lying along a rea...
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2014 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/11468 |
| Acceso en línea: | http://hdl.handle.net/10256/11468 |
| Access Level: | acceso embargado |
| Palabra clave: | Fotoquímica Photochemistry Química quàntica Quantum chemistry Química de l'estat excitat Excited state chemistry |
| Sumario: | The role of extended seams of conical intersection in excited-state mechanisms is reviewed. Seams are crossings of the potential energy surface in many dimensions where the decay from the excited to the ground state can occur, and the extended seam is composed of different segments lying along a reaction coordinate. Every segment is associated with a different primary photoproduct, which gives rise to competing pathways. This idea is first illustrated for fulvene and ethylene, and then it is used to explain more complex cases such as the dependence of the isomerisation of retinal chromophore isomers on the protein environment, the dependence of the efficiency of the azobenzene photochemical switch on the wavelength of irradiation and the direction of the isomerisation, and the coexistence of different mechanisms in the photo-induced Wolff rearrangement of diazonaphthoquinone. The role of extended seams in the photophysics of the DNA nucleobases and the relationship between two-state seams and three-state crossings is also discussed. As an outlook, the design of optical control strategies based on the passage of the excited molecule through the seam is considered, and it is shown how the excited-state lifetime of fulvene can be modulated by shaping the energy of the seam |
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