dc.contributor.author
Litman, Yair
dc.contributor.author
Rossi, Mariana
dc.date.accessioned
2020-12-14T15:31:56Z
dc.date.available
2020-12-14T15:31:56Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/29073
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-28823
dc.description.abstract
The nuclear tunneling crossover temperature (T-c) of hydrogen transfer reactions in supported molecular-switch architectures can lie close to room temperature. This calls for the inclusion of nuclear quantum effects (NQEs) in the calculation of reaction rates even at high temperatures. However, computations of NQEs relying on standard parametrized dimensionality-reduced models quickly become inadequate in these environments. In this Letter, we study the paradigmatic molecular switch based on porphycene molecules adsorbed on metallic surfaces with full-dimensional calculations that combine density-functional theory for the electrons with the semiclassical ring-polymer instanton approximation for the nuclei. We show that the double intramolecular hydrogen transfer (DHT) rate can be enhanced by orders of magnitude due to surface fluctuations in the deep-tunneling regime. We also explain the origin of an Arrhenius temperature dependence of the rate below T-c and why this dependence differs at different surfaces. We propose a simple model to rationalize the temperature dependence of DHT rates spanning diverse fcc [110] surfaces.
en
dc.format.extent
6 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by/4.0/
dc.subject
Physical Chemistry
en
dc.subject
Isotope effect
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.articlenumber
216001
dcterms.bibliographicCitation.doi
10.1103/PhysRevLett.125.216001
dcterms.bibliographicCitation.journaltitle
Physical Review Letters
dcterms.bibliographicCitation.number
21
dcterms.bibliographicCitation.volume
125
dcterms.bibliographicCitation.url
https://doi.org/10.1103/PhysRevLett.125.216001
refubium.affiliation
Biologie, Chemie, Pharmazie
refubium.affiliation.other
Institut für Chemie und Biochemie
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refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.issn
0031-9007
dcterms.isPartOf.eissn
1079-7114
refubium.resourceType.provider
WoS-Alert