Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices

Detalhes bibliográficos
Autor(a) principal: Maçôas, Ermelinda M. S.
Data de Publicação: 2004
Outros Autores: Khriachtchev, Leonid, Pettersson, Mika, Lundell, Jan, Fausto, Rui, Räsänen, Markku
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10316/5148
https://doi.org/10.1016/j.vibspec.2003.07.005
Resumo: An 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.
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spelling Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matricesVibrational excitationEnergy relaxationConformational interconversionMatrix-isolationAn 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.http://www.sciencedirect.com/science/article/B6THW-4B4VM27-1/1/deec31c3ec6aacc78547d2cb669840242004info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleaplication/PDFhttp://hdl.handle.net/10316/5148http://hdl.handle.net/10316/5148https://doi.org/10.1016/j.vibspec.2003.07.005engVibrational Spectroscopy. 34:1 (2004) 73-82Maçôas, Ermelinda M. S.Khriachtchev, LeonidPettersson, MikaLundell, JanFausto, RuiRäsänen, Markkuinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2020-11-06T16:59:25Zoai:estudogeral.uc.pt:10316/5148Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:19.775225Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
title Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
spellingShingle Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
Maçôas, Ermelinda M. S.
Vibrational excitation
Energy relaxation
Conformational interconversion
Matrix-isolation
title_short Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
title_full Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
title_fullStr Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
title_full_unstemmed Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
title_sort Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
author Maçôas, Ermelinda M. S.
author_facet Maçôas, Ermelinda M. S.
Khriachtchev, Leonid
Pettersson, Mika
Lundell, Jan
Fausto, Rui
Räsänen, Markku
author_role author
author2 Khriachtchev, Leonid
Pettersson, Mika
Lundell, Jan
Fausto, Rui
Räsänen, Markku
author2_role author
author
author
author
author
dc.contributor.author.fl_str_mv Maçôas, Ermelinda M. S.
Khriachtchev, Leonid
Pettersson, Mika
Lundell, Jan
Fausto, Rui
Räsänen, Markku
dc.subject.por.fl_str_mv Vibrational excitation
Energy relaxation
Conformational interconversion
Matrix-isolation
topic Vibrational excitation
Energy relaxation
Conformational interconversion
Matrix-isolation
description An 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.
publishDate 2004
dc.date.none.fl_str_mv 2004
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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dc.identifier.uri.fl_str_mv http://hdl.handle.net/10316/5148
http://hdl.handle.net/10316/5148
https://doi.org/10.1016/j.vibspec.2003.07.005
url http://hdl.handle.net/10316/5148
https://doi.org/10.1016/j.vibspec.2003.07.005
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Vibrational Spectroscopy. 34:1 (2004) 73-82
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dc.format.none.fl_str_mv aplication/PDF
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