Elucidating Redox-Level Dispersion and Local Dielectric Effects within Electroactive Molecular Films

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dc.contributor.authorBuono, Paulo R. [UNESP]
dc.contributor.authorDavis, Jason J.
dc.contributor.institutionUniversidade Estadual Paulista (Unesp)
dc.contributor.institutionUniv Oxford
dc.date.accessioned2014-12-03T13:08:55Z
dc.date.available2014-12-03T13:08:55Z
dc.date.issued2014-02-18
dc.description.abstractThe electron exchange between a redox-active molecular film and its underlying electrode can be cleanly tracked, in a frequency-resolved manner, through associated capacitive charging. If acquired data is treated with a classical (non quantum) model, mathematically equivalent to a Nernst distribution for one redox energy level, redox site coverage is both underestimated and environmentally variable. This physically unrealistic model fails to account for the energetic dispersion intrinsically related to the quantized characteristics of coupled redox and electrode states. If one maps this redox capacitive charging as a function of electrode potential one not only reproduces observations made by standard electroanalytical methods but additionally and directly resolves the spread of redox state energies the electrode is communicating with. In treating a population of surface-confined redox states as constituting a density of states, these analyses further resolve the effects of electrolyte dielectric on energetic spread in accordance with the electron-transfer models proposed by Marcus and others. These observations additionally underpin a directly (spectrally) resolved dispersion in electron-transfer kinetics.en
dc.description.affiliationUniv Estadual Paulista, Inst Quim, BR-14800900 Sao Paulo, Brazil
dc.description.affiliationUniv Oxford, Dept Chem, Oxford OX1 3QZ, England
dc.description.affiliationUnespUniv Estadual Paulista, Inst Quim, BR-14800900 Sao Paulo, Brazil
dc.description.sponsorshipFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.description.sponsorshipUNESP
dc.format.extent1997-2004
dc.identifierhttp://dx.doi.org/10.1021/ac4031708
dc.identifier.citationAnalytical Chemistry. Washington: Amer Chemical Soc, v. 86, n. 4, p. 1997-2004, 2014.
dc.identifier.doi10.1021/ac4031708
dc.identifier.issn0003-2700
dc.identifier.urihttp://hdl.handle.net/11449/111709
dc.identifier.wosWOS:000331775600012
dc.language.isoeng
dc.publisherAmer Chemical Soc
dc.relation.ispartofAnalytical Chemistry
dc.relation.ispartofjcr6.042
dc.relation.ispartofsjr2,362
dc.rights.accessRightsAcesso restrito
dc.sourceWeb of Science
dc.titleElucidating Redox-Level Dispersion and Local Dielectric Effects within Electroactive Molecular Filmsen
dc.typeArtigo
dcterms.rightsHolderAmer Chemical Soc

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