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• W2014741786 abstract "The photochemistry of a prototype push-pull merocyanine is discussed using a simple three-state model. As a derivative of butadiene, the model focuses on two isomerization reactions around the two double bonds of the butadiene backbone. As a molecule substituted by an electron donor and electron acceptor at opposite ends, its structure as well as its photochemistry are expected to be strongly affected by the environment. In polar solvents, a zwitterion transition state for each of the isomerization reactions is stabilized, and its energy is on the same order as that of the biradical one; this leads to the symmetry allowed crossing (S(0)/S(1) conical intersection). It is shown that applying an external electric field or varying the solvent polarity changes the relative energies of the different transition states as well as that of the conical intersection, and thus different photochemical products can be obtained. In particular, the very existence of conical intersections is found to depend on these external parameters. This work provides a theoretical foundation for ideas expressed by Squillacote et al. (J. Am. Chem. Soc. 2004, 126, 1940) concerning the electrostatic control of photochemical reactions." @default.
• W2014741786 created "2016-06-24" @default.
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• W2014741786 date "2009-08-14" @default.
• W2014741786 modified "2023-10-18" @default.
• W2014741786 title "Photoreactivity of a Push−Pull Merocyanine in Static Electric Fields: A Three-State Model of Isomerization Reactions Involving Conical Intersections" @default.
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• W2014741786 doi "https://doi.org/10.1021/jp904097k" @default.
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