On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings

Autores
Sánchez, Marina; Provasi, Patricio Federico; Aucar, Gustavo Adolfo; Sauer, Stephan P. A.
Año de publicación
2005
Idioma
inglés
Tipo de recurso
parte de libro
Estado
versión publicada
Descripción
Locally dense basis set were developed for correlated ab initio calculations of vicinal fluorine  fluorine indirect nuclear spin spin couplings in several saturated and unsaturated fluorinated hydrocarbons. We find that the choice of the basis set for each atom belonging to our studied model compounds depends on its location with respect to the coupled fluorine atoms and on the cis/trans or synperiplanar/antiperiplanar conformation of the molecule. Carbon atoms in the bonding path connecting the coupled fluorine atoms have to be described with better basis sets than the carbon atoms outside this path. For the hydrogen atoms directly connected to the coupling pathway in molecules with trans or antiperiplanar conformations and for all hydrogen atoms not directly connected to the coupling pathway one can employ a minimal basis set with only one s-function. Employing these type of LDBSs we can reduce the number of necessary basis functions by about 30% without losing more than about 1 Hz in accuracy. The analysis of the four contributions to the vicinal fluorine fluorine coupling constants shows that the non-contact orbital paramagnetic term is the most important contribution followed by the also non-contact spin-dipolar term. The Fermi contact term is the largest contribution only in the synperiplanar conformations of 1,2-difluoroethane and -propane. 
Fil: Sánchez, Marina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
Fil: Provasi, Patricio Federico. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Aucar, Gustavo Adolfo. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Sauer, Stephan P. A.. Universidad de Copenhagen; Dinamarca
Materia
LOCALLY DENSE BASIS SET
SSCC
NMR
LARGE BASIS SETS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/107847
Acceder
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network_name_str CONICET Digital (CONICET)
spelling On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine CouplingsSánchez, MarinaProvasi, Patricio FedericoAucar, Gustavo AdolfoSauer, Stephan P. A.LOCALLY DENSE BASIS SETSSCCNMRLARGE BASIS SETShttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Locally dense basis set were developed for correlated ab initio calculations of vicinal fluorine  fluorine indirect nuclear spin spin couplings in several saturated and unsaturated fluorinated hydrocarbons. We find that the choice of the basis set for each atom belonging to our studied model compounds depends on its location with respect to the coupled fluorine atoms and on the cis/trans or synperiplanar/antiperiplanar conformation of the molecule. Carbon atoms in the bonding path connecting the coupled fluorine atoms have to be described with better basis sets than the carbon atoms outside this path. For the hydrogen atoms directly connected to the coupling pathway in molecules with trans or antiperiplanar conformations and for all hydrogen atoms not directly connected to the coupling pathway one can employ a minimal basis set with only one s-function. Employing these type of LDBSs we can reduce the number of necessary basis functions by about 30% without losing more than about 1 Hz in accuracy. The analysis of the four contributions to the vicinal fluorine fluorine coupling constants shows that the non-contact orbital paramagnetic term is the most important contribution followed by the also non-contact spin-dipolar term. The Fermi contact term is the largest contribution only in the synperiplanar conformations of 1,2-difluoroethane and -propane. Fil: Sánchez, Marina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; ArgentinaFil: Provasi, Patricio Federico. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaFil: Aucar, Gustavo Adolfo. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Sauer, Stephan P. A.. Universidad de Copenhagen; DinamarcaElsevier IncSabin, J. R.2005info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/bookParthttp://purl.org/coar/resource_type/c_3248info:ar-repo/semantics/parteDeLibroapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/107847Sánchez, Marina; Provasi, Patricio Federico; Aucar, Gustavo Adolfo; Sauer, Stephan P. A.; On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings; Elsevier Inc; 48; 2005; 161-183978-0-12-034848-0CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0065327605480120info:eu-repo/semantics/altIdentifier/doi/10.1016/S0065-3276(05)48012-0info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/bookseries/advances-in-quantum-chemistry/vol/48/suppl/Cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:24:00Zoai:ri.conicet.gov.ar:11336/107847instacron: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:34982025-10-15 15:24:00.968CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
title On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
spellingShingle On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
Sánchez, Marina
LOCALLY DENSE BASIS SET
SSCC
NMR
LARGE BASIS SETS
title_short On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
title_full On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
title_fullStr On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
title_full_unstemmed On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
title_sort On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings
dc.creator.none.fl_str_mv Sánchez, Marina
Provasi, Patricio Federico
Aucar, Gustavo Adolfo
Sauer, Stephan P. A.
author Sánchez, Marina
author_facet Sánchez, Marina
Provasi, Patricio Federico
Aucar, Gustavo Adolfo
Sauer, Stephan P. A.
author_role author
author2 Provasi, Patricio Federico
Aucar, Gustavo Adolfo
Sauer, Stephan P. A.
author2_role author
author
author
dc.contributor.none.fl_str_mv Sabin, J. R.
dc.subject.none.fl_str_mv LOCALLY DENSE BASIS SET
SSCC
NMR
LARGE BASIS SETS
topic LOCALLY DENSE BASIS SET
SSCC
NMR
LARGE BASIS SETS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Locally dense basis set were developed for correlated ab initio calculations of vicinal fluorine  fluorine indirect nuclear spin spin couplings in several saturated and unsaturated fluorinated hydrocarbons. We find that the choice of the basis set for each atom belonging to our studied model compounds depends on its location with respect to the coupled fluorine atoms and on the cis/trans or synperiplanar/antiperiplanar conformation of the molecule. Carbon atoms in the bonding path connecting the coupled fluorine atoms have to be described with better basis sets than the carbon atoms outside this path. For the hydrogen atoms directly connected to the coupling pathway in molecules with trans or antiperiplanar conformations and for all hydrogen atoms not directly connected to the coupling pathway one can employ a minimal basis set with only one s-function. Employing these type of LDBSs we can reduce the number of necessary basis functions by about 30% without losing more than about 1 Hz in accuracy. The analysis of the four contributions to the vicinal fluorine fluorine coupling constants shows that the non-contact orbital paramagnetic term is the most important contribution followed by the also non-contact spin-dipolar term. The Fermi contact term is the largest contribution only in the synperiplanar conformations of 1,2-difluoroethane and -propane. 
Fil: Sánchez, Marina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina
Fil: Provasi, Patricio Federico. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; Argentina
Fil: Aucar, Gustavo Adolfo. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Sauer, Stephan P. A.. Universidad de Copenhagen; Dinamarca
description Locally dense basis set were developed for correlated ab initio calculations of vicinal fluorine  fluorine indirect nuclear spin spin couplings in several saturated and unsaturated fluorinated hydrocarbons. We find that the choice of the basis set for each atom belonging to our studied model compounds depends on its location with respect to the coupled fluorine atoms and on the cis/trans or synperiplanar/antiperiplanar conformation of the molecule. Carbon atoms in the bonding path connecting the coupled fluorine atoms have to be described with better basis sets than the carbon atoms outside this path. For the hydrogen atoms directly connected to the coupling pathway in molecules with trans or antiperiplanar conformations and for all hydrogen atoms not directly connected to the coupling pathway one can employ a minimal basis set with only one s-function. Employing these type of LDBSs we can reduce the number of necessary basis functions by about 30% without losing more than about 1 Hz in accuracy. The analysis of the four contributions to the vicinal fluorine fluorine coupling constants shows that the non-contact orbital paramagnetic term is the most important contribution followed by the also non-contact spin-dipolar term. The Fermi contact term is the largest contribution only in the synperiplanar conformations of 1,2-difluoroethane and -propane. 
publishDate 2005
dc.date.none.fl_str_mv 2005
dc.type.none.fl_str_mv info:eu-repo/semantics/publishedVersion
info:eu-repo/semantics/bookPart
http://purl.org/coar/resource_type/c_3248
info:ar-repo/semantics/parteDeLibro
status_str publishedVersion
format bookPart
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/107847
Sánchez, Marina; Provasi, Patricio Federico; Aucar, Gustavo Adolfo; Sauer, Stephan P. A.; On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings; Elsevier Inc; 48; 2005; 161-183
978-0-12-034848-0
CONICET Digital
CONICET
url http://hdl.handle.net/11336/107847
identifier_str_mv Sánchez, Marina; Provasi, Patricio Federico; Aucar, Gustavo Adolfo; Sauer, Stephan P. A.; On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin–Spin Coupling Constants: Vicinal Fluorine–Fluorine Couplings; Elsevier Inc; 48; 2005; 161-183
978-0-12-034848-0
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0065327605480120
info:eu-repo/semantics/altIdentifier/doi/10.1016/S0065-3276(05)48012-0
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/bookseries/advances-in-quantum-chemistry/vol/48/suppl/C
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Inc
publisher.none.fl_str_mv Elsevier Inc
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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score 13.22299

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