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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

AutorAndrés, José Luis; Merchán, Manuela; Acuña, A. Ulises ; Frutos, L. M.; Castaño, Obis
Palabras claveOrganic compounds
Potential energy surfaces
Triplet state
Ground states
Molecular configurations
Fecha de publicación15-ene-2004
EditorAmerican Institute of Physics
CitaciónJ.Chem.Phys. 120, 1208-1216(2004)
ResumenTriplet 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).
Versión del editorhttp://link.aip.org/link/?JCPSA6/120/1208/1
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