Please use this identifier to cite or link to this item: https://hdl.handle.net/10316/109090
DC FieldValueLanguage
dc.contributor.authorApóstolo, R. F. G.-
dc.contributor.authorBento, R. R. F.-
dc.contributor.authorFausto, Rui-
dc.date.accessioned2023-09-27T09:42:07Z-
dc.date.available2023-09-27T09:42:07Z-
dc.date.issued2015-
dc.identifier.issn00111643pt
dc.identifier.issn1334417Xpt
dc.identifier.urihttps://hdl.handle.net/10316/109090-
dc.description.abstractThe monomeric form of trichloroacetic acid (CCl3COOH; TCA) was isolated in a cryogenic nitrogen matrix (15 K) and the higher energy trans conformer (O=C–O–H dihedral: 180°) was generated in situ by narrowband near-infrared selective excitation the 1st OH stretching overtone of the low-energy cis conformer (O=C–O–H dihedral: 0°). The spontaneous decay, by tunneling, of the generated high-energy conformer into the cis form was then evaluated and compared with those observed previously for the trans conformers of acetic and formic acids in identical experimental conditions. The much faster decay of the high-energy conformer of TCA compared to both formic and acetic acids (by ~35 and ca. 25 times, respectively) was found to correlate well with the lower energy barrier for the trans → cis isomerization in the studied compound. The experimental studies received support from quantum chemistry calculations undertaken at the DFT(B3LYP)/cc-pVDZ level of approximation, which allowed a detailed characterization of the potential energy surface of the molecule and the detailed assignment of the infrared spectra of the two conformers.pt
dc.language.isoengpt
dc.publisherCroatian Chemical Societypt
dc.relationFCT project PEst-OE/QUI/UI0313/2014pt
dc.relationScholarship from CAPES Foundation (Proc. no. BEX 2010/14-3)pt
dc.rightsopenAccesspt
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/pt
dc.subjecttrichloroacetic acidpt
dc.subjectNIR-induced in situ generation of the higher energy trans-TCA conformerpt
dc.subjectspontaneous decay by tunnelingpt
dc.subjectmatrix-isolation infrared spectroscopypt
dc.subjectquantum chemical calculationspt
dc.titleNarrowband NIR-Induced In Situ Generation of the High-Energy Trans Conformer of Trichloroacetic Acid Isolated in Solid Nitrogen and its Spontaneous Decay by Tunneling to the Low-Energy Cis Conformerpt
dc.typearticle-
degois.publication.firstPage377pt
degois.publication.lastPage386pt
degois.publication.issue4pt
degois.publication.titleCroatica Chemica Actapt
dc.peerreviewedyespt
dc.identifier.doi10.5562/cca2704pt
degois.publication.volume88pt
dc.date.embargo2015-01-01*
uc.date.periodoEmbargo0pt
item.cerifentitytypePublications-
item.languageiso639-1en-
item.fulltextCom Texto completo-
item.grantfulltextopen-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.openairetypearticle-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.orcid0000-0002-8264-6854-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
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