Infrared-induced conformational interconversion in carboxylic acids isolated in low-temperature rare-gas matrices
Autor(a) principal: | |
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Data de Publicação: | 2004 |
Outros Autores: | , , , , |
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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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 |
format |
article |
status_str |
publishedVersion |
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 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
aplication/PDF |
dc.source.none.fl_str_mv |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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