{ "dc.contributor.author": "Voityuk, Alexander A." , "dc.date.accessioned": "2011-03-29T08:44:31Z" , "dc.date.available": "2010-12-14T12:56:56Z" , "dc.date.available": "2011-03-29T08:44:31Z" , "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" , "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.rights.accessRights": "info:eu-repo/semantics/openAccess" , "dc.identifier.doi": "http://dx.doi.org/10.1063/1.2166232" , "dc.identifier.eissn": "1089-7690" }