Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model

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dc.contributor.author Voityuk, Alexander A.
dc.date.issued 2006
dc.identifier.citation Voityuk, A.A. (2006). Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model. Journal of Chemical Physics, 124 (6), 064505. Recuperat 29 març 2011,a http://link.aip.org/link/doi/10.1063/1.2166232
dc.identifier.issn 0021-9606 (versió paper)
dc.identifier.issn 1089-7690 (versió electrònica)
dc.identifier.uri http://hdl.handle.net/10256/3317
dc.description.abstract Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽ da = (E2 - E1) μ12 Rda + (2 E3 - E1 - E2) 2 μ13 μ23 Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model
dc.format.mimetype application/pdf
dc.language.iso eng
dc.publisher American Institute of Physics
dc.relation.isformatof Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.2166232
dc.relation.ispartof © Journal of Chemical Physics, 2006, vol. 124, núm. 6
dc.relation.ispartofseries Articles publicats (D-Q)
dc.rights Tots els drets reservats
dc.subject Anàlisi numèrica
dc.subject Electrònica molecular
dc.subject Models matemàtics
dc.subject Transferència de càrrega
dc.subject Charge transfer
dc.subject Mathematical models
dc.subject Molecular electronics
dc.subject Numerical analysis
dc.title Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model
dc.type info:eu-repo/semantics/article
dc.identifier.doi http://dx.doi.org/10.1063/1.2166232


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