Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/5091
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dc.contributor.authorArnaut, Luís G.-
dc.contributor.authorFormosinho, Sebastião J.-
dc.contributor.authorBarroso, Mónica-
dc.date.accessioned2008-09-01T15:03:48Z-
dc.date.available2008-09-01T15:03:48Z-
dc.date.issued2006en_US
dc.identifier.citationJournal of Molecular Structure. 786:2-3 (2006) 207-214en_US
dc.identifier.urihttp://hdl.handle.net/10316/5091-
dc.description.abstractThe reaction path of the interacting-state model with the Lippincott-Schroeder potential for hydrogen bonds, is used in transition-state theory calculations with the semiclassical correction for tunnelling (LS-ISM/scTST) to estimate proton and hydrogen-atom transfer rates at low temperatures. Down to 100 K, the semiclassical correction leads to semi-empirical rates and isotope effects that are in good agreement with the thermal tautomerism of porphine, and the excited-state tautomerisms of salicylideneanilines and 2-(2'-hydroxyphenyl)benzoxazole. For lower temperatures, the tunnelling corrections become extremely high and unreliable. It is shown that the permeability of an Eckart barrier fitted to the curvature of the LS-ISM reaction path leads to good estimates of these reaction rates down to 2 K.en_US
dc.description.urihttp://www.sciencedirect.com/science/article/B6TGS-4HM82TC-1/1/4f3417d1e9b73a409dac8ef57fa0d35ben_US
dc.format.mimetypeaplication/PDFen
dc.language.isoengeng
dc.rightsopenAccesseng
dc.subjectTunnellingen_US
dc.subjectProton transferen_US
dc.subjectHydrogen atom transferen_US
dc.subjectTautomerismen_US
dc.titleTunnelling in low-temperature hydrogen-atom and proton transfersen_US
dc.typearticleen_US
uc.controloAutoridadeSim-
item.fulltextCom Texto completo-
item.languageiso639-1en-
item.grantfulltextopen-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.orcid0000-0002-3223-4819-
crisitem.author.orcid0000-0001-6607-0026-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
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