The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings

Autores
Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo
Año de publicación
2007
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Working within relativistic polarization propagator approach, it was shown in a previous article that the electronic origin of diamagnetic contributions to NMR nuclear magnetic shielding, σdσd, are mostly excitations that fit in a well defined interval of energies such that 2mc2≦(εi−εs¯)<4mc22mc2≦(εi−εs¯)<4mc2. That interval of energies does not have, in principle, any physical reason to be so well defined, and gives a large amount of the total contribution to σdσd, e.g., close to 98% of it. Then a further study is given in this article, where we show some of the main characteristics of that interval of energy, such as its universal appearance and basis set independence. Our main result is the finding that σdσd is completely described by that interval of excitation energies, i.e., there is no contribution arising from outside of it. Most of the contributions belonging to that interval arise from virtual electronic energies larger than −3mc2−3mc2. For heavier atoms, there are few contributions from states with virtual negative energies smaller than −3mc2−3mc2. The model systems under study were noble gases, XH (X=BrX=Br, I, and At), XH2XH2 (X=OX=O, S, Se, Te, and Po), XH3XH3 (X=NX=N, P, As, Sb, and Bi); XH4XH4 (X=SnX=Sn and Pb), and SnXH3SnXH3 (X=BrX=Br and I). The pattern of contributions of occupied molecular orbitals (MOs) is also shown, where the 1s1∕21s1∕2 is the most important for excitations ending in the bottom half part of the above mentioned interval. On the other hand, the contribution of the other occupied MOs are more important than that of 1s1∕21s1∕2 for the other part of such interval. We also show that σdσd is electron correlation independent within both relativistic and nonrelativistic domain. In the case of σpσp, we find out a clear dependence of electron correlation effects with relativistic effects, which is of the order of 30% for Pb in PbH4PbH4.
Fil: Maldonado, Alejandro Fabián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Nordeste; Argentina
Fil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Nordeste; Argentina
Materia
INTERVAL OF ENERGIES
DIAMAGNETIC SHIELDING
THEORY OF RELATIVITY
MAGNETIC SHIELDING
LEAD
ELECTRON CORRELATION CALCULATIONS
DIAMAGNETISM
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:11336/24675

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oai_identifier_str oai:ri.conicet.gov.ar:11336/24675
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldingsMaldonado, Alejandro FabiánAucar, Gustavo AdolfoINTERVAL OF ENERGIESDIAMAGNETIC SHIELDINGTHEORY OF RELATIVITYMAGNETIC SHIELDINGLEADELECTRON CORRELATION CALCULATIONSDIAMAGNETISMhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Working within relativistic polarization propagator approach, it was shown in a previous article that the electronic origin of diamagnetic contributions to NMR nuclear magnetic shielding, σdσd, are mostly excitations that fit in a well defined interval of energies such that 2mc2≦(εi−εs¯)<4mc22mc2≦(εi−εs¯)<4mc2. That interval of energies does not have, in principle, any physical reason to be so well defined, and gives a large amount of the total contribution to σdσd, e.g., close to 98% of it. Then a further study is given in this article, where we show some of the main characteristics of that interval of energy, such as its universal appearance and basis set independence. Our main result is the finding that σdσd is completely described by that interval of excitation energies, i.e., there is no contribution arising from outside of it. Most of the contributions belonging to that interval arise from virtual electronic energies larger than −3mc2−3mc2. For heavier atoms, there are few contributions from states with virtual negative energies smaller than −3mc2−3mc2. The model systems under study were noble gases, XH (X=BrX=Br, I, and At), XH2XH2 (X=OX=O, S, Se, Te, and Po), XH3XH3 (X=NX=N, P, As, Sb, and Bi); XH4XH4 (X=SnX=Sn and Pb), and SnXH3SnXH3 (X=BrX=Br and I). The pattern of contributions of occupied molecular orbitals (MOs) is also shown, where the 1s1∕21s1∕2 is the most important for excitations ending in the bottom half part of the above mentioned interval. On the other hand, the contribution of the other occupied MOs are more important than that of 1s1∕21s1∕2 for the other part of such interval. We also show that σdσd is electron correlation independent within both relativistic and nonrelativistic domain. In the case of σpσp, we find out a clear dependence of electron correlation effects with relativistic effects, which is of the order of 30% for Pb in PbH4PbH4.Fil: Maldonado, Alejandro Fabián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Nordeste; ArgentinaFil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Nordeste; ArgentinaAmerican Institute of Physics2007-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/24675Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings; American Institute of Physics; Journal of Chemical Physics; 127; 15; 12-2007; 154115-1541230021-96061089-7690CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://aip.scitation.org/doi/10.1063/1.2787003info:eu-repo/semantics/altIdentifier/doi/10.1063/1.2787003info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:39:31Zoai:ri.conicet.gov.ar:11336/24675instacron: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 09:39:32.151CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
title The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
spellingShingle The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
Maldonado, Alejandro Fabián
INTERVAL OF ENERGIES
DIAMAGNETIC SHIELDING
THEORY OF RELATIVITY
MAGNETIC SHIELDING
LEAD
ELECTRON CORRELATION CALCULATIONS
DIAMAGNETISM
title_short The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
title_full The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
title_fullStr The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
title_full_unstemmed The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
title_sort The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings
dc.creator.none.fl_str_mv Maldonado, Alejandro Fabián
Aucar, Gustavo Adolfo
author Maldonado, Alejandro Fabián
author_facet Maldonado, Alejandro Fabián
Aucar, Gustavo Adolfo
author_role author
author2 Aucar, Gustavo Adolfo
author2_role author
dc.subject.none.fl_str_mv INTERVAL OF ENERGIES
DIAMAGNETIC SHIELDING
THEORY OF RELATIVITY
MAGNETIC SHIELDING
LEAD
ELECTRON CORRELATION CALCULATIONS
DIAMAGNETISM
topic INTERVAL OF ENERGIES
DIAMAGNETIC SHIELDING
THEORY OF RELATIVITY
MAGNETIC SHIELDING
LEAD
ELECTRON CORRELATION CALCULATIONS
DIAMAGNETISM
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Working within relativistic polarization propagator approach, it was shown in a previous article that the electronic origin of diamagnetic contributions to NMR nuclear magnetic shielding, σdσd, are mostly excitations that fit in a well defined interval of energies such that 2mc2≦(εi−εs¯)<4mc22mc2≦(εi−εs¯)<4mc2. That interval of energies does not have, in principle, any physical reason to be so well defined, and gives a large amount of the total contribution to σdσd, e.g., close to 98% of it. Then a further study is given in this article, where we show some of the main characteristics of that interval of energy, such as its universal appearance and basis set independence. Our main result is the finding that σdσd is completely described by that interval of excitation energies, i.e., there is no contribution arising from outside of it. Most of the contributions belonging to that interval arise from virtual electronic energies larger than −3mc2−3mc2. For heavier atoms, there are few contributions from states with virtual negative energies smaller than −3mc2−3mc2. The model systems under study were noble gases, XH (X=BrX=Br, I, and At), XH2XH2 (X=OX=O, S, Se, Te, and Po), XH3XH3 (X=NX=N, P, As, Sb, and Bi); XH4XH4 (X=SnX=Sn and Pb), and SnXH3SnXH3 (X=BrX=Br and I). The pattern of contributions of occupied molecular orbitals (MOs) is also shown, where the 1s1∕21s1∕2 is the most important for excitations ending in the bottom half part of the above mentioned interval. On the other hand, the contribution of the other occupied MOs are more important than that of 1s1∕21s1∕2 for the other part of such interval. We also show that σdσd is electron correlation independent within both relativistic and nonrelativistic domain. In the case of σpσp, we find out a clear dependence of electron correlation effects with relativistic effects, which is of the order of 30% for Pb in PbH4PbH4.
Fil: Maldonado, Alejandro Fabián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Nordeste; Argentina
Fil: Aucar, Gustavo Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Nordeste; Argentina
description Working within relativistic polarization propagator approach, it was shown in a previous article that the electronic origin of diamagnetic contributions to NMR nuclear magnetic shielding, σdσd, are mostly excitations that fit in a well defined interval of energies such that 2mc2≦(εi−εs¯)<4mc22mc2≦(εi−εs¯)<4mc2. That interval of energies does not have, in principle, any physical reason to be so well defined, and gives a large amount of the total contribution to σdσd, e.g., close to 98% of it. Then a further study is given in this article, where we show some of the main characteristics of that interval of energy, such as its universal appearance and basis set independence. Our main result is the finding that σdσd is completely described by that interval of excitation energies, i.e., there is no contribution arising from outside of it. Most of the contributions belonging to that interval arise from virtual electronic energies larger than −3mc2−3mc2. For heavier atoms, there are few contributions from states with virtual negative energies smaller than −3mc2−3mc2. The model systems under study were noble gases, XH (X=BrX=Br, I, and At), XH2XH2 (X=OX=O, S, Se, Te, and Po), XH3XH3 (X=NX=N, P, As, Sb, and Bi); XH4XH4 (X=SnX=Sn and Pb), and SnXH3SnXH3 (X=BrX=Br and I). The pattern of contributions of occupied molecular orbitals (MOs) is also shown, where the 1s1∕21s1∕2 is the most important for excitations ending in the bottom half part of the above mentioned interval. On the other hand, the contribution of the other occupied MOs are more important than that of 1s1∕21s1∕2 for the other part of such interval. We also show that σdσd is electron correlation independent within both relativistic and nonrelativistic domain. In the case of σpσp, we find out a clear dependence of electron correlation effects with relativistic effects, which is of the order of 30% for Pb in PbH4PbH4.
publishDate 2007
dc.date.none.fl_str_mv 2007-12
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/11336/24675
Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings; American Institute of Physics; Journal of Chemical Physics; 127; 15; 12-2007; 154115-154123
0021-9606
1089-7690
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24675
identifier_str_mv Maldonado, Alejandro Fabián; Aucar, Gustavo Adolfo; The appearance of an interval of energies that contain the whole diamagnetic contributions to NMR magnetic shieldings; American Institute of Physics; Journal of Chemical Physics; 127; 15; 12-2007; 154115-154123
0021-9606
1089-7690
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://aip.scitation.org/doi/10.1063/1.2787003
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.2787003
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
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
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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