Show simple item record

dc.contributor.author
Fang, Wei
dc.contributor.author
Heller, Eric R.
dc.contributor.author
Richardson, Jeremy O.
dc.date.accessioned
2023-10-24T08:40:31Z
dc.date.available
2023-10-04T07:20:18Z
dc.date.available
2023-10-05T08:18:24Z
dc.date.available
2023-10-24T08:40:31Z
dc.date.issued
2023-10-21
dc.identifier.issn
2041-6520
dc.identifier.issn
2041-6539
dc.identifier.other
10.1039/d3sc03706a
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/634900
dc.identifier.doi
10.3929/ethz-b-000634900
dc.description.abstract
Thermally activated chemical reactions are typically understood in terms of overcoming potential-energy barriers. However, standard rate theories break down in the presence of a conical intersection (CI) because these processes are inherently nonadiabatic, invalidating the Born-Oppenheimer approximation. Moreover, CIs give rise to intricate nuclear quantum effects such as tunnelling and the geometric phase, which are neglected by standard trajectory-based simulations and remain largely unexplored in complex molecular systems. We present new semiclassical transition-state theories based on an extension of golden-rule instanton theory to describe nonadiabatic tunnelling through CIs and thus provide an intuitive picture for the reaction mechanism. We apply the method in conjunction with first-principles electronic-structure calculations to the electron transfer in the bis(methylene)-adamantyl cation. Our study reveals a strong competition between heavy-atom tunnelling and geometric-phase effects.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
Royal Society of Chemistry
en_US
dc.rights.uri
http://creativecommons.org/licenses/by/3.0/
dc.title
Competing quantum effects in heavy-atom tunnelling through conical intersections
en_US
dc.type
Journal Article
dc.rights.license
Creative Commons Attribution 3.0 Unported
dc.date.published
2023-09-27
ethz.journal.title
Chemical Science
ethz.journal.volume
14
en_US
ethz.journal.issue
39
en_US
ethz.journal.abbreviated
Chem. Sci.
ethz.pages.start
10777
en_US
ethz.pages.end
10785
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.grant
Nonadiabatic effects in chemical reactions
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Cambridge
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.::02543 - Inst. f. Molekulare Physikalische Wiss. / Institute of Molecular Physical Science::09602 - Richardson, Jeremy / Richardson, Jeremy
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.::02543 - Inst. f. Molekulare Physikalische Wiss. / Institute of Molecular Physical Science::09602 - Richardson, Jeremy / Richardson, Jeremy
ethz.grant.agreementno
207772
ethz.grant.fundername
SNF
ethz.grant.funderDoi
10.13039/501100001711
ethz.grant.program
Projekte MINT
ethz.date.deposited
2023-10-04T07:20:22Z
ethz.source
WOS
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2024-02-03T05:40:48Z
ethz.rosetta.lastUpdated
2024-02-03T05:40:48Z
ethz.rosetta.versionExported
true
ethz.COinS
ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.atitle=Competing%20quantum%20effects%20in%20heavy-atom%20tunnelling%20through%20conical%20intersections&rft.jtitle=Chemical%20Science&rft.date=2023-10-21&rft.volume=14&rft.issue=39&rft.spage=10777&rft.epage=10785&rft.issn=2041-6520&2041-6539&rft.au=Fang,%20Wei&Heller,%20Eric%20R.&Richardson,%20Jeremy%20O.&rft.genre=article&rft_id=info:doi/10.1039/d3sc03706a&
 Search print copy at ETH Library

Files in this item

Thumbnail

Publication type

Show simple item record