Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane

Autores
Romanini, Michela; Mitsari, Efstratia; Tripathi, Pragya; Serra, Pablo; Zuriaga, Mariano Jose; Tamarit, Josep Lluis; Macovez, Roberto
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The molecular dynamics in the ambient-pressure solid phase of 1,1,2-trichloroethane is studied by means of broadband dielectric spectroscopy and molecular dynamics simulations. The dielectric spectra of polycrystalline samples obtained by crystallization from the liquid phase exhibit, besides a space-charge relaxation associated with accumulation of charges at crystalline domain boundaries, two loss features arising from dipolar molecular relaxations. The most prominent and slower of the two loss features is identified as a configurational leap of the molecules which involves a simultaneous change in spatial orientation and structural conformation, namely between two isomeric forms (gauche+ and gauche-) of opposite chirality. In this peculiar dynamic process, the positions of the three chlorine atoms in the crystal lattice remain unchanged, while those of the carbon and hydrogen atoms are modified. This dynamic process is responsible for the disorder observed in an earlier X-ray diffraction study and confirmed by our simulation, which is present only at temperatures relatively close to the melting point, starting 40 K below. The onset of the disorder is visible as an anomaly in the temperature dependence of the dc conductivity of the sample at exactly the same temperature. While the slower relaxation dynamics (combined isomerization/reorientation) becomes increasingly more intense on approaching the melting point, the faster dynamics exhibits significantly lower but constant dielectric strength. On the basis of our molecular dynamics simulations, we assign the faster relaxation to large fluctuations of the molecular dipole moments, partly due to large-angle librations of the chloroethane species.
Fil: Romanini, Michela. Universidad Politécnica de Catalunya; España
Fil: Mitsari, Efstratia. Universidad Politécnica de Catalunya; España
Fil: Tripathi, Pragya. Universidad Politécnica de Catalunya; España
Fil: Serra, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Zuriaga, Mariano Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Tamarit, Josep Lluis. Universidad Politécnica de Catalunya; España
Fil: Macovez, Roberto. Universidad Politécnica de Catalunya; España
Materia
MOLECULAR CRYSTALS
CHIRALITY
MOLECULAR DYNAMICS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/91671
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/91671
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-TrichloroethaneRomanini, MichelaMitsari, EfstratiaTripathi, PragyaSerra, PabloZuriaga, Mariano JoseTamarit, Josep LluisMacovez, RobertoMOLECULAR CRYSTALSCHIRALITYMOLECULAR DYNAMICShttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The molecular dynamics in the ambient-pressure solid phase of 1,1,2-trichloroethane is studied by means of broadband dielectric spectroscopy and molecular dynamics simulations. The dielectric spectra of polycrystalline samples obtained by crystallization from the liquid phase exhibit, besides a space-charge relaxation associated with accumulation of charges at crystalline domain boundaries, two loss features arising from dipolar molecular relaxations. The most prominent and slower of the two loss features is identified as a configurational leap of the molecules which involves a simultaneous change in spatial orientation and structural conformation, namely between two isomeric forms (gauche+ and gauche-) of opposite chirality. In this peculiar dynamic process, the positions of the three chlorine atoms in the crystal lattice remain unchanged, while those of the carbon and hydrogen atoms are modified. This dynamic process is responsible for the disorder observed in an earlier X-ray diffraction study and confirmed by our simulation, which is present only at temperatures relatively close to the melting point, starting 40 K below. The onset of the disorder is visible as an anomaly in the temperature dependence of the dc conductivity of the sample at exactly the same temperature. While the slower relaxation dynamics (combined isomerization/reorientation) becomes increasingly more intense on approaching the melting point, the faster dynamics exhibits significantly lower but constant dielectric strength. On the basis of our molecular dynamics simulations, we assign the faster relaxation to large fluctuations of the molecular dipole moments, partly due to large-angle librations of the chloroethane species.Fil: Romanini, Michela. Universidad Politécnica de Catalunya; EspañaFil: Mitsari, Efstratia. Universidad Politécnica de Catalunya; EspañaFil: Tripathi, Pragya. Universidad Politécnica de Catalunya; EspañaFil: Serra, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; ArgentinaFil: Zuriaga, Mariano Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; ArgentinaFil: Tamarit, Josep Lluis. Universidad Politécnica de Catalunya; EspañaFil: Macovez, Roberto. Universidad Politécnica de Catalunya; EspañaAmerican Chemical Society2018-03-22info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/91671Romanini, Michela; Mitsari, Efstratia; Tripathi, Pragya; Serra, Pablo; Zuriaga, Mariano Jose; et al.; Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane; American Chemical Society; Journal of Physical Chemistry C; 122; 10; 22-3-2018; 5774-57831932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.jpcc.7b12469info:eu-repo/semantics/altIdentifier/arxiv/https://arxiv.org/abs/1802.09857info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.7b12469info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:56:06Zoai:ri.conicet.gov.ar:11336/91671instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:56:06.719CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
title Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
spellingShingle Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
Romanini, Michela
MOLECULAR CRYSTALS
CHIRALITY
MOLECULAR DYNAMICS
title_short Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
title_full Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
title_fullStr Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
title_full_unstemmed Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
title_sort Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane
dc.creator.none.fl_str_mv Romanini, Michela
Mitsari, Efstratia
Tripathi, Pragya
Serra, Pablo
Zuriaga, Mariano Jose
Tamarit, Josep Lluis
Macovez, Roberto
author Romanini, Michela
author_facet Romanini, Michela
Mitsari, Efstratia
Tripathi, Pragya
Serra, Pablo
Zuriaga, Mariano Jose
Tamarit, Josep Lluis
Macovez, Roberto
author_role author
author2 Mitsari, Efstratia
Tripathi, Pragya
Serra, Pablo
Zuriaga, Mariano Jose
Tamarit, Josep Lluis
Macovez, Roberto
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv MOLECULAR CRYSTALS
CHIRALITY
MOLECULAR DYNAMICS
topic MOLECULAR CRYSTALS
CHIRALITY
MOLECULAR DYNAMICS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The molecular dynamics in the ambient-pressure solid phase of 1,1,2-trichloroethane is studied by means of broadband dielectric spectroscopy and molecular dynamics simulations. The dielectric spectra of polycrystalline samples obtained by crystallization from the liquid phase exhibit, besides a space-charge relaxation associated with accumulation of charges at crystalline domain boundaries, two loss features arising from dipolar molecular relaxations. The most prominent and slower of the two loss features is identified as a configurational leap of the molecules which involves a simultaneous change in spatial orientation and structural conformation, namely between two isomeric forms (gauche+ and gauche-) of opposite chirality. In this peculiar dynamic process, the positions of the three chlorine atoms in the crystal lattice remain unchanged, while those of the carbon and hydrogen atoms are modified. This dynamic process is responsible for the disorder observed in an earlier X-ray diffraction study and confirmed by our simulation, which is present only at temperatures relatively close to the melting point, starting 40 K below. The onset of the disorder is visible as an anomaly in the temperature dependence of the dc conductivity of the sample at exactly the same temperature. While the slower relaxation dynamics (combined isomerization/reorientation) becomes increasingly more intense on approaching the melting point, the faster dynamics exhibits significantly lower but constant dielectric strength. On the basis of our molecular dynamics simulations, we assign the faster relaxation to large fluctuations of the molecular dipole moments, partly due to large-angle librations of the chloroethane species.
Fil: Romanini, Michela. Universidad Politécnica de Catalunya; España
Fil: Mitsari, Efstratia. Universidad Politécnica de Catalunya; España
Fil: Tripathi, Pragya. Universidad Politécnica de Catalunya; España
Fil: Serra, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Zuriaga, Mariano Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Tamarit, Josep Lluis. Universidad Politécnica de Catalunya; España
Fil: Macovez, Roberto. Universidad Politécnica de Catalunya; España
description The molecular dynamics in the ambient-pressure solid phase of 1,1,2-trichloroethane is studied by means of broadband dielectric spectroscopy and molecular dynamics simulations. The dielectric spectra of polycrystalline samples obtained by crystallization from the liquid phase exhibit, besides a space-charge relaxation associated with accumulation of charges at crystalline domain boundaries, two loss features arising from dipolar molecular relaxations. The most prominent and slower of the two loss features is identified as a configurational leap of the molecules which involves a simultaneous change in spatial orientation and structural conformation, namely between two isomeric forms (gauche+ and gauche-) of opposite chirality. In this peculiar dynamic process, the positions of the three chlorine atoms in the crystal lattice remain unchanged, while those of the carbon and hydrogen atoms are modified. This dynamic process is responsible for the disorder observed in an earlier X-ray diffraction study and confirmed by our simulation, which is present only at temperatures relatively close to the melting point, starting 40 K below. The onset of the disorder is visible as an anomaly in the temperature dependence of the dc conductivity of the sample at exactly the same temperature. While the slower relaxation dynamics (combined isomerization/reorientation) becomes increasingly more intense on approaching the melting point, the faster dynamics exhibits significantly lower but constant dielectric strength. On the basis of our molecular dynamics simulations, we assign the faster relaxation to large fluctuations of the molecular dipole moments, partly due to large-angle librations of the chloroethane species.
publishDate 2018
dc.date.none.fl_str_mv 2018-03-22
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/91671
Romanini, Michela; Mitsari, Efstratia; Tripathi, Pragya; Serra, Pablo; Zuriaga, Mariano Jose; et al.; Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane; American Chemical Society; Journal of Physical Chemistry C; 122; 10; 22-3-2018; 5774-5783
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/91671
identifier_str_mv Romanini, Michela; Mitsari, Efstratia; Tripathi, Pragya; Serra, Pablo; Zuriaga, Mariano Jose; et al.; Simultaneous Orientational and Conformational Molecular Dynamics in Solid 1,1,2-Trichloroethane; American Chemical Society; Journal of Physical Chemistry C; 122; 10; 22-3-2018; 5774-5783
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.jpcc.7b12469
info:eu-repo/semantics/altIdentifier/arxiv/https://arxiv.org/abs/1802.09857
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.7b12469
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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