Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/10295
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dc.contributor.authorCosta, Sílvia M. B.-
dc.contributor.authorMaçanita, A. L.-
dc.contributor.authorFormosinho, S. J.-
dc.date.accessioned2009-06-24T10:12:31Z-
dc.date.available2009-06-24T10:12:31Z-
dc.date.issued1984-08-
dc.identifier.citationThe Journal of Physical Chemistry. 88:18 (1984) 4089-4095en_US
dc.identifier.urihttp://hdl.handle.net/10316/10295-
dc.description.abstractA study of intermolecular, exothermic charge-transfer interactions is described. A distance dependence on the unimolecular charge-transfer rate constant k,,(R) is observed in viscous solvents where transfer at longer distances than the collisional one can compete with dissociation of an encounter complex. A comparative study of the quenching phenomena, occurring in a family of redox partners of aromatic esters and amines, was carried out in nonviscous solvents (hexane and acetonitrile) and viscous solvents (liquid paraffin/heptane mixtures and nonionic micelles of Triton X- 100). In the latter, the experimental reactional distances obtained are discussed in terms of effective distances R,ff, which are related to an average value of kct(Reff) for the reactant pair distribution function. A correlation of these distances with either the free activation energy, Act, or the diffusion coefficient D enables the estimation of an order of magnitude of parameters such as the average radii of donor and acceptor orbitals, L = (2.7 f 0.2) X cm, a preexponential factor at the collisional distance, k’,,(R,) = 3.7 X 10” d, an intrinsic reorganization parameter X = 0.64 eV, and an electronic matrix element V(Rc) N eV for the nonpolar media studied. An equation for kct(R), k,,(R) = koct(R,)e xp[-2(R - R,)/L] exp(-AG*/kB7+),d erived within the framework of a semiclassical theory, is used to discuss these interactions as equally nonadiabatic reactions to which an extended Marcus formalism is applied.en_US
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsopenAccesseng
dc.titleEffective distances of exothermic charge-transfer reactions in the excited stateen_US
dc.typearticleen_US
dc.identifier.doi10.1021/j150662a047-
uc.controloAutoridadeSim-
item.grantfulltextopen-
item.languageiso639-1en-
item.fulltextCom Texto completo-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.orcid0000-0003-0976-6654-
crisitem.author.orcid0000-0001-6607-0026-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
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