Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243)
Autor(a) principal: | |
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Data de Publicação: | 2008 |
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/10316/10423 https://doi.org/10.1021/jp807388a |
Resumo: | The molecular structure and infrared spectrum of the atmospheric pollutant 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243) were characterized experimentally and theoretically. The theoretical calculations show the existence of two conformers, with the gauche (G) and trans (T) orientation around the HCCC dihedral angle. Conformer G was calculated to be more stable than form T by more than 10 kJ mol−1. In consonance with the large predicted relative energy of conformer T, only the G form was identified spectroscopically in cryogenic argon (10 K) and xenon (20 K) matrices prepared from room-temperature equilibrium vapor of the compound. The observed infrared spectra of the matrix-isolated HCFC-243 were interpreted with the aid of high-level density functional theory calculations and normal coordinate analysis. For experimental identification of the weakest IR absorption bands, the spectrum of HCFC-243 in the neat solid state at 145 K was obtained. This spectrum also confirmed the sole presence of the G conformer in the sample. Natural bond orbital and atomic charge analyses were carried out for the two conformers to shed light on the most important intramolecular interactions in the two conformers, in particular those responsible for their relative stability. |
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Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243)The molecular structure and infrared spectrum of the atmospheric pollutant 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243) were characterized experimentally and theoretically. The theoretical calculations show the existence of two conformers, with the gauche (G) and trans (T) orientation around the HCCC dihedral angle. Conformer G was calculated to be more stable than form T by more than 10 kJ mol−1. In consonance with the large predicted relative energy of conformer T, only the G form was identified spectroscopically in cryogenic argon (10 K) and xenon (20 K) matrices prepared from room-temperature equilibrium vapor of the compound. The observed infrared spectra of the matrix-isolated HCFC-243 were interpreted with the aid of high-level density functional theory calculations and normal coordinate analysis. For experimental identification of the weakest IR absorption bands, the spectrum of HCFC-243 in the neat solid state at 145 K was obtained. This spectrum also confirmed the sole presence of the G conformer in the sample. Natural bond orbital and atomic charge analyses were carried out for the two conformers to shed light on the most important intramolecular interactions in the two conformers, in particular those responsible for their relative stability.American Chemical Society2008-11-20info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/10423http://hdl.handle.net/10316/10423https://doi.org/10.1021/jp807388aengThe Journal of Physical Chemistry A. 112:46 (2008) 11641-116481089-5639Lucena Jr., J. R.Sharma, A.Reva, I. D.Araújo, R. M. C. U.Ventura, E.Monte, S. A. doBraga, C. F.Ramos, M. N.Fausto, R.info: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:RCAAP2021-10-26T13:22:05ZPortal AgregadorONG |
dc.title.none.fl_str_mv |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) |
title |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) |
spellingShingle |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) Lucena Jr., J. R. |
title_short |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) |
title_full |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) |
title_fullStr |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) |
title_full_unstemmed |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) |
title_sort |
Matrix Isolation FTIR Spectroscopic and Theoretical Study of 3,3-Dichloro-1,1,1-Trifluoropropane (HCFC-243) |
author |
Lucena Jr., J. R. |
author_facet |
Lucena Jr., J. R. Sharma, A. Reva, I. D. Araújo, R. M. C. U. Ventura, E. Monte, S. A. do Braga, C. F. Ramos, M. N. Fausto, R. |
author_role |
author |
author2 |
Sharma, A. Reva, I. D. Araújo, R. M. C. U. Ventura, E. Monte, S. A. do Braga, C. F. Ramos, M. N. Fausto, R. |
author2_role |
author author author author author author author author |
dc.contributor.author.fl_str_mv |
Lucena Jr., J. R. Sharma, A. Reva, I. D. Araújo, R. M. C. U. Ventura, E. Monte, S. A. do Braga, C. F. Ramos, M. N. Fausto, R. |
description |
The molecular structure and infrared spectrum of the atmospheric pollutant 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243) were characterized experimentally and theoretically. The theoretical calculations show the existence of two conformers, with the gauche (G) and trans (T) orientation around the HCCC dihedral angle. Conformer G was calculated to be more stable than form T by more than 10 kJ mol−1. In consonance with the large predicted relative energy of conformer T, only the G form was identified spectroscopically in cryogenic argon (10 K) and xenon (20 K) matrices prepared from room-temperature equilibrium vapor of the compound. The observed infrared spectra of the matrix-isolated HCFC-243 were interpreted with the aid of high-level density functional theory calculations and normal coordinate analysis. For experimental identification of the weakest IR absorption bands, the spectrum of HCFC-243 in the neat solid state at 145 K was obtained. This spectrum also confirmed the sole presence of the G conformer in the sample. Natural bond orbital and atomic charge analyses were carried out for the two conformers to shed light on the most important intramolecular interactions in the two conformers, in particular those responsible for their relative stability. |
publishDate |
2008 |
dc.date.none.fl_str_mv |
2008-11-20 |
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/10316/10423 http://hdl.handle.net/10316/10423 https://doi.org/10.1021/jp807388a |
url |
http://hdl.handle.net/10316/10423 https://doi.org/10.1021/jp807388a |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
The Journal of Physical Chemistry A. 112:46 (2008) 11641-11648 1089-5639 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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repository.mail.fl_str_mv |
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_version_ |
1777302686414143488 |