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Voityuk, Alexander A. | |
2006 | |
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 | |
application/pdf | |
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 | |
0021-9606 (versió paper) 1089-7690 (versió electrònica) |
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http://hdl.handle.net/10256/3317 | |
eng | |
American Institute of Physics | |
Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.2166232 Articles publicats (D-Q) |
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© Journal of Chemical Physics, 2006, vol. 124, núm. 6 | |
Tots els drets reservats | |
Anà lisi numèrica
Electrònica molecular Models matemà tics Transferència de cà rrega Charge transfer Mathematical models Molecular electronics Numerical analysis |
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Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model | |
info:eu-repo/semantics/article | |
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