On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide

Autores
Sánchez, Marina; Alkorta, Ibon; Elguero, José; Ferraro, Marta Beatriz; Sauer, Stephan P. A.
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculated as mixed linear response functions of the electric and magnetic dipole moment operators. Applying a canonical transformation of the Hamiltonian, which reformulates the magnetic dipole moment operator in terms of the operator for the torque acting on the electrons, the ORP of a molecule can be partitioned into atomic and group contributions. In the present work, we investigate the transferability of such individual contributions in a series of small, chiral molecules: hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide. The isotropic atomic or group contributions have been evaluated for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules.
Fil: Sánchez, Marina. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; España
Fil: Alkorta, Ibon. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; España
Fil: Elguero, José. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; España
Fil: Ferraro, Marta Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Sauer, Stephan P. A.. Universidad de Copenhagen; Dinamarca
Materia
Chirality
Optical Rotatory Power
Atomic Contributions
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:11336/18021
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxideSánchez, MarinaAlkorta, IbonElguero, JoséFerraro, Marta BeatrizSauer, Stephan P. A.ChiralityOptical Rotatory PowerAtomic Contributionshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculated as mixed linear response functions of the electric and magnetic dipole moment operators. Applying a canonical transformation of the Hamiltonian, which reformulates the magnetic dipole moment operator in terms of the operator for the torque acting on the electrons, the ORP of a molecule can be partitioned into atomic and group contributions. In the present work, we investigate the transferability of such individual contributions in a series of small, chiral molecules: hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide. The isotropic atomic or group contributions have been evaluated for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules.Fil: Sánchez, Marina. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; EspañaFil: Alkorta, Ibon. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; EspañaFil: Elguero, José. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; EspañaFil: Ferraro, Marta Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Sauer, Stephan P. A.. Universidad de Copenhagen; DinamarcaTaylor & Francis2014-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/18021Sánchez, Marina; Alkorta, Ibon; Elguero, José; Ferraro, Marta Beatriz; Sauer, Stephan P. A.; On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide; Taylor & Francis; Molecular Physics; 112; 12; 9-2014; 1624-16320026-8976enginfo:eu-repo/semantics/altIdentifier/doi/10.1080/00268976.2013.851420info:eu-repo/semantics/altIdentifier/url/http://www.tandfonline.com/doi/full/10.1080/00268976.2013.851420info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:27:54Zoai:ri.conicet.gov.ar:11336/18021instacron: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:34982025-09-29 10:27:54.792CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
title On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
spellingShingle On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
Sánchez, Marina
Chirality
Optical Rotatory Power
Atomic Contributions
title_short On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
title_full On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
title_fullStr On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
title_full_unstemmed On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
title_sort On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
dc.creator.none.fl_str_mv Sánchez, Marina
Alkorta, Ibon
Elguero, José
Ferraro, Marta Beatriz
Sauer, Stephan P. A.
author Sánchez, Marina
author_facet Sánchez, Marina
Alkorta, Ibon
Elguero, José
Ferraro, Marta Beatriz
Sauer, Stephan P. A.
author_role author
author2 Alkorta, Ibon
Elguero, José
Ferraro, Marta Beatriz
Sauer, Stephan P. A.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Chirality
Optical Rotatory Power
Atomic Contributions
topic Chirality
Optical Rotatory Power
Atomic Contributions
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 chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculated as mixed linear response functions of the electric and magnetic dipole moment operators. Applying a canonical transformation of the Hamiltonian, which reformulates the magnetic dipole moment operator in terms of the operator for the torque acting on the electrons, the ORP of a molecule can be partitioned into atomic and group contributions. In the present work, we investigate the transferability of such individual contributions in a series of small, chiral molecules: hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide. The isotropic atomic or group contributions have been evaluated for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules.
Fil: Sánchez, Marina. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; España
Fil: Alkorta, Ibon. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; España
Fil: Elguero, José. Consejo Superior de Investigaciones Científicas. Instituto de Química Medica; España
Fil: Ferraro, Marta Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Sauer, Stephan P. A.. Universidad de Copenhagen; Dinamarca
description The chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculated as mixed linear response functions of the electric and magnetic dipole moment operators. Applying a canonical transformation of the Hamiltonian, which reformulates the magnetic dipole moment operator in terms of the operator for the torque acting on the electrons, the ORP of a molecule can be partitioned into atomic and group contributions. In the present work, we investigate the transferability of such individual contributions in a series of small, chiral molecules: hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide. The isotropic atomic or group contributions have been evaluated for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules.
publishDate 2014
dc.date.none.fl_str_mv 2014-09
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/11336/18021
Sánchez, Marina; Alkorta, Ibon; Elguero, José; Ferraro, Marta Beatriz; Sauer, Stephan P. A.; On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide; Taylor & Francis; Molecular Physics; 112; 12; 9-2014; 1624-1632
0026-8976
url http://hdl.handle.net/11336/18021
identifier_str_mv Sánchez, Marina; Alkorta, Ibon; Elguero, José; Ferraro, Marta Beatriz; Sauer, Stephan P. A.; On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide; Taylor & Francis; Molecular Physics; 112; 12; 9-2014; 1624-1632
0026-8976
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1080/00268976.2013.851420
info:eu-repo/semantics/altIdentifier/url/http://www.tandfonline.com/doi/full/10.1080/00268976.2013.851420
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 Taylor & Francis
publisher.none.fl_str_mv Taylor & Francis
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 13.070432

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