A 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-cyclooctatetraene
NAGIOS: RODERIC FUNCIONANDO

A 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-cyclooctatetraene

DSpace Repository

A 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-cyclooctatetraene

Show simple item record

dc.contributor.author Frutos, Luis Manuel
dc.contributor.author Castaño, Obis
dc.contributor.author Andrés, José Luis
dc.contributor.author Merchán Bonete, Manuela
dc.contributor.author Acuña Fernández, Alberto Ulises
dc.date.accessioned 2010-06-14T09:29:33Z
dc.date.available 2010-06-14T09:29:33Z
dc.date.issued 2004
dc.identifier.uri http://hdl.handle.net/10550/12961
dc.language.iso en en
dc.relation http://scitation.aip.org/getpdf/servlet/GetPDFServlet?filetype=pdf&id=JCPSA6000120000003001208000001&idtype=cvips&prog=normal&doi= en
dc.source A 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-cyclooctatetraene en
dc.subject Organic compounds ; Potential energy surfaces ; Triplet state ; Ground states ; Molecular configurations en
dc.title A 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-cyclooctatetraene en
dc.type info:eu-repo/semantics/article en
dc.type info:eu-repo/semantics/publishedVersion en
dc.subject.unesco UNESCO::FÍSICA::Química física en
dc.identifier.doi 10.1063/1.1631418 en
dc.description.abstractenglish Triplet 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 γ = (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 C�C bond stretchings and C–C bond torsions, which collectively change the ground-state COT bent conformation (D2d) toward a planar triplet state (D8h). en
dc.description.private manuela.merchan@uv.es en

View       (453.4Kb)

This item appears in the following Collection(s)

Show simple item record

Search DSpace

Advanced Search

Browse

Statistics