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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/24675
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oai:ri.conicet.gov.ar:11336/24675 |
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repository_id_str |
3498 |
network_name_str |
CONICET Digital (CONICET) |
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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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1844613250897936384 |
score |
13.070432 |