Journal
CHEMPHYSCHEM
Volume 15, Issue 15, Pages 3166-3181Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201402359
Keywords
extended seams; isomerization; photochemistry; photophysics; reaction mechanisms
Funding
- Spanish Ministerio de Economia y Competividad (MINECO) [CTQ2011-26573]
- Catalan Agencia de Gestio d'Ajuts Universitaris i de Recerca (AGAUR) [SGR0528]
- MINECO [UNGI08-4E-003, UNGI10-4E-801]
- European Fund for Regional Development (FEDER)
- Xarxa de Referencia en Quimica Teorica i Computacional de Catalunya from AGAUR
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available