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dc.contributor.authorAndrés, José Luis-
dc.contributor.authorMerchán, Manuela-
dc.contributor.authorAcuña, A. Ulises-
dc.contributor.authorFrutos, L. M.-
dc.contributor.authorCastaño, Obis-
dc.date.accessioned2009-03-20T10:29:15Z-
dc.date.available2009-03-20T10:29:15Z-
dc.date.issued2004-01-15-
dc.identifier.citationJ.Chem.Phys. 120, 1208-1216(2004)en_US
dc.identifier.issn0021-9606-
dc.identifier.urihttp://hdl.handle.net/10261/11756-
dc.description.abstractTriplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of "nonvertical" behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion parameter у=(2g²/κ₁)1/2 in which g stands for the norm of the energy gradient in the PES of the acceptor triplet state and κ₁ is a combination of vibrational force constants of the ground-state acceptor in the gradient direction. The application of the model to existing experimental data for the triplet energy transfer reaction to COT from a series of π,π* triplet donors, provides a detailed interpretation of the parameters that determine the transfer rate constant. In addition, the model shows that the observed decrease of the acceptor electronic excitation energy is due to thermal activation of CC bond stretchings and C–C bond torsions, which collectively change the ground-state COT bent conformation (D2d) toward a planar triplet state (D8h).en_US
dc.description.sponsorshipWork financed by Projects BQU2000/1500, BQU2000/0646, BQU2001/2926 from the Spanish Ministry of Science and Technology ~MCyT!. L.M.F. is grateful to the Ministry of Education, Culture and Sport ~Spain! for a Doctoral Fellowship.en_US
dc.format.extent453491 bytes-
dc.format.mimetypeapplication/pdf-
dc.language.isoengen_US
dc.publisherAmerican Institute of Physicsen_US
dc.rightsopenAccessen_US
dc.subjectOrganic compoundsen_US
dc.subjectPotential energy surfacesen_US
dc.subjectTriplet stateen_US
dc.subjectGround statesen_US
dc.subjectMolecular configurationsen_US
dc.titleA theory of nonvertical triplet energy transfer in terms of accurate potential energy surfaces: The transfer reaction from π,π* triplet donors to 1,3,5,7 -cyclooctatetraeneen_US
dc.typeartículoen_US
dc.identifier.doi10.1063/1.1631418-
dc.description.peerreviewedPeer revieweden_US
dc.relation.publisherversionhttp://link.aip.org/link/?JCPSA6/120/1208/1en_US
dc.relation.publisherversionhttp://dx.doi.org/10.1063/1.1631418en_US
dc.type.coarhttp://purl.org/coar/resource_type/c_6501es_ES
item.openairetypeartículo-
item.cerifentitytypePublications-
item.languageiso639-1en-
item.grantfulltextopen-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.fulltextWith Fulltext-
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