Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/5148
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dc.contributor.authorMaçôas, Ermelinda M. S.-
dc.contributor.authorKhriachtchev, Leonid-
dc.contributor.authorPettersson, Mika-
dc.contributor.authorLundell, Jan-
dc.contributor.authorFausto, Rui-
dc.contributor.authorRäsänen, Markku-
dc.date.accessioned2008-09-01T15:04:46Z-
dc.date.available2008-09-01T15:04:46Z-
dc.date.issued2004en_US
dc.identifier.citationVibrational Spectroscopy. 34:1 (2004) 73-82en_US
dc.identifier.urihttp://hdl.handle.net/10316/5148-
dc.description.abstractAn overview of our recent studies dealing with infrared-induced conformational interconversion of carboxylic acids isolated in rare-gas matrices is presented. Extensive rotational photoisomerization studies have been performed on formic acid, which is the simplest organic acid enabling this kind of processes. Formic acid has two conformers and interconversion between them can be induced by vibrational excitation. As such, it is an ideal model system to study the conformational dynamics of the carboxylic group. Formic acid molecules were found to be isolated in different local environments within the rare-gas matrices, as shown by the site splitting of the vibrational bands. Narrowband tunable infrared (IR) radiation was used to induce site-selective isomerization processes. The induced changes in the IR absorption spectra allowed for a detailed analysis of the vibrational properties of both conformers of formic acid isolated in solid argon. In particular, derived from the intermode coupling constants the local environment was shown to affects the intramolecular potential energy surface. Tunneling is involved in the rotamerization of formic acid, with the tunneling rate being affected by the local environment. Additionally, formic acid exhibits isomer-selective photodissociation where narrowband IR excitation can control the conformer-dependent photodissociation channels. Tunable IR radiation was also used to promote rotamerization in a series of matrix-isolated dicarboxylic acids (ethanedioic, propanedioic, and 2-butenedioic acids) by exciting the first overtone of the O---H stretching mode or a suitable combination mode at similar energies. Efficient isomerization involving rotation around the C---O bond was observed in most cases whereas the internal rotation around the C---C bond was found to be constrained for ethanedioic and (Z)-2-butenedioic acids.en_US
dc.description.urihttp://www.sciencedirect.com/science/article/B6THW-4B4VM27-1/1/deec31c3ec6aacc78547d2cb66984024en_US
dc.format.mimetypeaplication/PDFen
dc.language.isoengeng
dc.rightsopenAccesseng
dc.subjectVibrational excitationen_US
dc.subjectEnergy relaxationen_US
dc.subjectConformational interconversionen_US
dc.subjectMatrix-isolationen_US
dc.titleInfrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matricesen_US
dc.typearticleen_US
item.fulltextCom Texto completo-
item.grantfulltextopen-
item.languageiso639-1en-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.orcid0000-0002-8264-6854-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
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