dc.contributor.author
Grandjean, Alexander
dc.contributor.author
Pérez Lustres, J. Luis
dc.contributor.author
Jung, Gregor
dc.date.accessioned
2022-01-03T12:16:40Z
dc.date.available
2022-01-03T12:16:40Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/33007
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-32731
dc.description.abstract
Intermolecular Proton Transfer (PT) dynamics can be best studied by optical spectroscopy, which can cover the vast timescale spanned by the process. PT in a hydrogen bonding complex between a pyranine-based photoacid and a trialkyl-phosphine oxide is addressed. The photoreaction is traced with the help of femtosecond transient absorption and picosecond-resolved fluorescence. Characteristic kinetics and spectra of the intervening species are isolated by global analysis and spectral decomposition of time-resolved fluorescence. It is found that the shared proton shifts towards the phosphine site upon photoexcitation in acetonitrile. The process occurs on the sub-picosecond timescale, essentially, under solvent control. Despite the ultrafast rate, an equilibrium between the complex and the hydrogen-bonded ion pair (HBIP) is established. Further reaction steps are delayed to the nanosecond timescale, where formation of the excited deprotonated form is observed. The far-reaching consistency between the various methods supports an irreversible Eigen-Weller mechanism in the excited state.
en
dc.format.extent
12 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by-nc/4.0/
dc.subject
Eigen-Weller model
en
dc.subject
excited states
en
dc.subject
proton transfer
en
dc.subject
solvent relaxation
en
dc.subject
transient absorption spectroscopy
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
Solvent-Controlled Intermolecular Proton-Transfer Follows an Irreversible Eigen-Weller Model from fs to ns
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.doi
10.1002/cptc.202100177
dcterms.bibliographicCitation.journaltitle
ChemPhotoChem
dcterms.bibliographicCitation.number
12
dcterms.bibliographicCitation.pagestart
1094
dcterms.bibliographicCitation.pageend
1105
dcterms.bibliographicCitation.volume
5
dcterms.bibliographicCitation.url
https://doi.org/10.1002/cptc.202100177
refubium.affiliation
Physik
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.eissn
2367-0932
refubium.resourceType.provider
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