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dc.contributor.author
Litman, Yair
dc.contributor.author
Richardson, Jeremy O.
dc.contributor.author
Kumagai, Takashi
dc.contributor.author
Rossi, Mariana
dc.date.accessioned
2019-02-25T11:35:08Z
dc.date.available
2019-02-21T06:22:26Z
dc.date.available
2019-02-25T11:35:08Z
dc.date.issued
2019-02-13
dc.identifier.other
10.1021/jacs.8b12471
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/326540
dc.identifier.doi
10.3929/ethz-b-000326540
dc.description.abstract
We address the double hydrogen transfer (DHT) dynamics of the porphycene molecule, a complex paradigmatic system in which the making and breaking of H-bonds in a highly anharmonic potential energy surface require a quantum mechanical treatment not only of the electrons but also of the nuclei. We combine density functional theory calculations, employing hybrid functionals and van der Waals corrections, with recently proposed and optimized path-integral ring-polymer methods for the approximation of quantum vibrational spectra and reaction rates. Our full-dimensional ring-polymer instanton simulations show that below 100 K the concerted DHT tunneling pathway dominates but between 100 and 300 K there is a competition between concerted and stepwise pathways when nuclear quantum effects are included. We obtain ground-state reaction rates of 2.19 × 1011 s–1 at 150 K and 0.63 × 1011 s–1 at 100 K, in good agreement with experiment. We also reproduce the puzzling N–H stretching band of porphycene with very good accuracy from thermostated ring-polymer molecular dynamics simulations. The position and line shape of this peak, centered at around 2600 cm–1 and spanning 750 cm–1, stem from a combination of very strong H-bonds, the coupling to low-frequency modes, and the access to cis-like isomeric conformations, which cannot be appropriately captured with classical-nuclei dynamics. These results verify the appropriateness of our general theoretical approach and provide a framework for a deeper physical understanding of hydrogen transfer dynamics in complex systems.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
American Chemical Society
en_US
dc.rights.uri
http://creativecommons.org/licenses/by/4.0/
dc.title
Elucidating the Nuclear Quantum Dynamics of Intramolecular Double Hydrogen Transfer in Porphycene
en_US
dc.type
Journal Article
dc.rights.license
Creative Commons Attribution 4.0 International
dc.date.published
2019-01-16
ethz.journal.title
Journal of the American Chemical Society
ethz.journal.volume
141
en_US
ethz.journal.issue
6
en_US
ethz.pages.start
2526
en_US
ethz.pages.end
2534
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Washington, DC
en_US
ethz.publication.status
published
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02515 - Laboratorium für Physikalische Chemie / Laboratory of Physical Chemistry::09602 - Richardson, Jeremy / Richardson, Jeremy
en_US
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02515 - Laboratorium für Physikalische Chemie / Laboratory of Physical Chemistry::09602 - Richardson, Jeremy / Richardson, Jeremy
ethz.date.deposited
2019-02-21T06:22:28Z
ethz.source
SCOPUS
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2019-02-25T11:35:19Z
ethz.rosetta.lastUpdated
2019-02-25T11:35:19Z
ethz.rosetta.exportRequired
true
ethz.rosetta.versionExported
true
ethz.COinS
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