Publikation:

Diffusion, spin and reaction control in geminate reverse electron transfer

Lade...
Vorschaubild

Datum

2001

Autor:innen

Burshtein, Anatoly I.
Krissinel, Evgenii B.

Herausgeber:innen

Kontakt

ISSN der Zeitschrift

Electronic ISSN

ISBN

Bibliografische Daten

Verlag

Schriftenreihe

Auflagebezeichnung

DOI (zitierfähiger Link)
ArXiv-ID

Internationale Patentnummer

Angaben zur Forschungsförderung

Projekt

Open Access-Veröffentlichung
Open Access Green
Core Facility der Universität Konstanz

Gesperrt bis

Titel in einer weiteren Sprache

Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published

Erschienen in

Physical Chemistry, Chemical Physics. 2001, 3(2), pp. 198-203. ISSN 1463-9076. eISSN 1463-9084. Available under: doi: 10.1039/B006586M

Zusammenfassung

Kinetic analyses of geminate radical escape yields in terms of a simple (exponential) reaction scheme with first-order rate constants of separation and geminate recombination have been widely used in the literature, e.g. to evaluate rate constants of reverse electron transfer (k et). Here we demonstrate the limited value of such rate constants by formally analysing, in terms of the exponential model, the diffusion coefficient (υiz. viscosity) dependence of the radical escape yield as theoretically calculated in the framework of diffusion-dependent electron transfer theory (unified treatment of non-contact photoinduced forward and geminate reverse electron transfer). It is shown that, while the true electron transfer rate constant is kept constant, the apparent rate constant k et from the exponential model undergoes a wide variation as a function of diffusion coefficient and the rate of spin conversion. Nevertheless, the function k et(D) represented in a double log plot for various rates of spin conversion provides a useful map suitable to assign characteristic regions of diffusional, spin and reaction control of the geminate process. As an application to real systems the experimental example of the [Ru(bpy)3]2+/methylviologen system is reconsidered. Here a magnetic field effect on the k et(D) dependence is useful to corroborate the non-contact formation of the radical pair in the photochemical forward electron transfer reaction.

Zusammenfassung in einer weiteren Sprache

Fachgebiet (DDC)
540 Chemie

Schlagwörter

Konferenz

Rezension
undefined / . - undefined, undefined

Forschungsvorhaben

Organisationseinheiten

Zeitschriftenheft

Zugehörige Datensätze in KOPS

Zitieren

ISO 690BURSHTEIN, Anatoly I., Evgenii B. KRISSINEL, Ulrich STEINER, 2001. Diffusion, spin and reaction control in geminate reverse electron transfer. In: Physical Chemistry, Chemical Physics. 2001, 3(2), pp. 198-203. ISSN 1463-9076. eISSN 1463-9084. Available under: doi: 10.1039/B006586M
BibTex
@article{Burshtein2001Diffu-9746,
  year={2001},
  doi={10.1039/B006586M},
  title={Diffusion, spin and reaction control in geminate reverse electron transfer},
  number={2},
  volume={3},
  issn={1463-9076},
  journal={Physical Chemistry, Chemical Physics},
  pages={198--203},
  author={Burshtein, Anatoly I. and Krissinel, Evgenii B. and Steiner, Ulrich}
}
RDF
<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/9746">
    <dc:creator>Burshtein, Anatoly I.</dc:creator>
    <dc:creator>Krissinel, Evgenii B.</dc:creator>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:format>application/pdf</dc:format>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/9746/1/Diffusion_spin_and_reaction_control_in_geminate_reverse_electron_transfer.pdf"/>
    <dc:rights>Attribution-NonCommercial-NoDerivs 2.0 Generic</dc:rights>
    <dc:contributor>Krissinel, Evgenii B.</dc:contributor>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T18:14:07Z</dc:date>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dcterms:abstract xml:lang="eng">Kinetic analyses of geminate radical escape yields in terms of a simple (exponential) reaction scheme with first-order rate constants of separation and geminate recombination have been widely used in the literature, e.g. to evaluate rate constants of reverse electron transfer (k et). Here we demonstrate the limited value of such rate constants by formally analysing, in terms of the exponential model, the diffusion coefficient (υiz. viscosity) dependence of the radical escape yield as theoretically calculated in the framework of diffusion-dependent electron transfer theory (unified treatment of non-contact photoinduced forward and geminate reverse electron transfer). It is shown that, while the true electron transfer rate constant is kept constant, the apparent rate constant k et from the exponential model undergoes a wide variation as a function of diffusion coefficient and the rate of spin conversion. Nevertheless, the function k et(D) represented in a double log plot for various rates of spin conversion provides a useful map suitable to assign characteristic regions of diffusional, spin and reaction control of the geminate process. As an application to real systems the experimental example of the [Ru(bpy)3]2+/methylviologen system is reconsidered. Here a magnetic field effect on the k et(D) dependence is useful to corroborate the non-contact formation of the radical pair in the photochemical forward electron transfer reaction.</dcterms:abstract>
    <dc:language>eng</dc:language>
    <dcterms:issued>2001</dcterms:issued>
    <dc:contributor>Burshtein, Anatoly I.</dc:contributor>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/9746/1/Diffusion_spin_and_reaction_control_in_geminate_reverse_electron_transfer.pdf"/>
    <dcterms:rights rdf:resource="http://creativecommons.org/licenses/by-nc-nd/2.0/"/>
    <dc:contributor>Steiner, Ulrich</dc:contributor>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/9746"/>
    <dcterms:bibliographicCitation>First publ. in: Physical Chemistry, Chemical Physics 3 (2001), pp. 198-203</dcterms:bibliographicCitation>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T18:14:07Z</dcterms:available>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dcterms:title>Diffusion, spin and reaction control in geminate reverse electron transfer</dcterms:title>
    <dc:creator>Steiner, Ulrich</dc:creator>
  </rdf:Description>
</rdf:RDF>

Interner Vermerk

xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter

Kontakt
URL der Originalveröffentl.

Prüfdatum der URL

Prüfungsdatum der Dissertation

Finanzierungsart

Kommentar zur Publikation

Allianzlizenz
Corresponding Authors der Uni Konstanz vorhanden
Internationale Co-Autor:innen
Universitätsbibliographie
Nein
Begutachtet
Diese Publikation teilen