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dc.contributor.authorBeyer, ANen
dc.contributor.authorRichardson, JOen
dc.contributor.authorKnowles, PJen
dc.contributor.authorRommel, Judithen
dc.contributor.authorAlthorpe, Stuarten
dc.date.accessioned2017-01-16T14:28:15Z
dc.date.available2017-01-16T14:28:15Z
dc.date.issued2016-11-03en
dc.identifier.issn1948-7185
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/261883
dc.description.abstractThe instanton method obtains approximate tunneling rates from the minimum-action path (known as the instanton) linking reactants to the products at a given temperature. An efficient way to find the instanton is to search for saddle-points on the ring-polymer potential surface, which is obtained by expressing the quantum Boltzmann operator as a discrete path-integral. Here we report a practical implementation of this ring-polymer form of instanton theory into the Molpro electronic-structure package, which allows the rates to be computed on-the-fly, without the need for a fitted analytic potential-energy surface. As a test case, we compute tunneling rates for the benchmark H + CH₄ reaction, showing how the efficiency of the instanton method allows the user systematically to converge the tunneling rate with respect to the level of electronic-structure theory.
dc.description.sponsorshipA.N.B., J.O.R., and S.C.A. acknowledge funding from the UK Engineering and Physics Sciences Research Council. J.O.R. was supported by a European Union COFUND/Durham Junior Research Fellowship. J.B.R. thanks the Alexander von Humboldt Foundation for a Fedor-Lynen Fellowship.
dc.languageengen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.titleQuantum Tunneling Rates of Gas-Phase Reactions from On-the-Fly Instanton Calculations.en
dc.typeArticle
prism.endingPage4379
prism.issueIdentifier21en
prism.publicationDate2016en
prism.publicationNameThe Journal of Physical Chemistry Lettersen
prism.startingPage4374
prism.volume7en
dc.identifier.doi10.17863/CAM.7116
dcterms.dateAccepted2016-10-19en
rioxxterms.versionofrecord10.1021/acs.jpclett.6b02115en
rioxxterms.versionVoRen
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/en
rioxxterms.licenseref.startdate2016-11-03en
dc.contributor.orcidAlthorpe, Stuart [0000-0003-1288-8070]
dc.identifier.eissn1948-7185
rioxxterms.typeJournal Article/Reviewen
cam.issuedOnline2016-10-19en
cam.orpheus.successThu Jan 30 10:20:25 GMT 2020 - The item has an open VoR version.*
rioxxterms.freetoread.startdate2100-01-01


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International