Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs
In this work, a new approach to studying coupling pathways for the Fermi contact term of NMR spin-spin coupling constants (SSCCs) is presented. It is based on the known form of propagating the Fermi hole through a canonical molecular orbital (CMO). It requires having an adequate spatial description...
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Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v114_n2_p1044_Contreras http://hdl.handle.net/20.500.12110/paper_10895639_v114_n2_p1044_Contreras |
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paper:paper_10895639_v114_n2_p1044_Contreras2023-06-08T16:06:27Z Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs Contreras, Rubén Horacio Fermi contact Fermi contact term Fermi holes Lone pair Natural bond orbital New approaches NMR spectroscopy Space transmission Spatial descriptions Spin-spin coupling constants Chemical bonds Molecular modeling Molecular orbitals Nuclear magnetic resonance Nuclear magnetic resonance spectroscopy Spin dynamics Fermions organophosphorus compound phosphorus phosphorus derivative algorithm article chemical structure chemistry conformation methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory Algorithms Magnetic Resonance Spectroscopy Models, Molecular Molecular Conformation Organophosphorus Compounds Phosphorus Phosphorus Compounds Physicochemical Phenomena Quantum Theory In this work, a new approach to studying coupling pathways for the Fermi contact term of NMR spin-spin coupling constants (SSCCs) is presented. It is based on the known form of propagating the Fermi hole through a canonical molecular orbital (CMO). It requires having an adequate spatial description of the relevant canonical molecular orbitals, which are obtained by expanding CMOs in terms of natural bond orbitals (NBOs). For detecting the relevant contributions of CMOs to a given Fermi contact (FC) pathway, the description of the FC in terms of the triplet polarization propagator (PP) is used. To appreciate the potential of this approach, dubbed FCCP-CMO (Fermi contact coupling pathways-CMO), it is applied to analyze the through-space transmission of the FC term of JPP SSCCs by overlap of the P lone pairs. This method can be applied using well-known quantum chemistry software without any further modification, which makes it appealing for use as a complement to SSCC measurements by NMR spectroscopy. © 2010 American Chemical Society. Fil:Contreras, R.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2010 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v114_n2_p1044_Contreras http://hdl.handle.net/20.500.12110/paper_10895639_v114_n2_p1044_Contreras |
institution |
Universidad de Buenos Aires |
institution_str |
I-28 |
repository_str |
R-134 |
collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
topic |
Fermi contact Fermi contact term Fermi holes Lone pair Natural bond orbital New approaches NMR spectroscopy Space transmission Spatial descriptions Spin-spin coupling constants Chemical bonds Molecular modeling Molecular orbitals Nuclear magnetic resonance Nuclear magnetic resonance spectroscopy Spin dynamics Fermions organophosphorus compound phosphorus phosphorus derivative algorithm article chemical structure chemistry conformation methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory Algorithms Magnetic Resonance Spectroscopy Models, Molecular Molecular Conformation Organophosphorus Compounds Phosphorus Phosphorus Compounds Physicochemical Phenomena Quantum Theory |
spellingShingle |
Fermi contact Fermi contact term Fermi holes Lone pair Natural bond orbital New approaches NMR spectroscopy Space transmission Spatial descriptions Spin-spin coupling constants Chemical bonds Molecular modeling Molecular orbitals Nuclear magnetic resonance Nuclear magnetic resonance spectroscopy Spin dynamics Fermions organophosphorus compound phosphorus phosphorus derivative algorithm article chemical structure chemistry conformation methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory Algorithms Magnetic Resonance Spectroscopy Models, Molecular Molecular Conformation Organophosphorus Compounds Phosphorus Phosphorus Compounds Physicochemical Phenomena Quantum Theory Contreras, Rubén Horacio Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs |
topic_facet |
Fermi contact Fermi contact term Fermi holes Lone pair Natural bond orbital New approaches NMR spectroscopy Space transmission Spatial descriptions Spin-spin coupling constants Chemical bonds Molecular modeling Molecular orbitals Nuclear magnetic resonance Nuclear magnetic resonance spectroscopy Spin dynamics Fermions organophosphorus compound phosphorus phosphorus derivative algorithm article chemical structure chemistry conformation methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory Algorithms Magnetic Resonance Spectroscopy Models, Molecular Molecular Conformation Organophosphorus Compounds Phosphorus Phosphorus Compounds Physicochemical Phenomena Quantum Theory |
description |
In this work, a new approach to studying coupling pathways for the Fermi contact term of NMR spin-spin coupling constants (SSCCs) is presented. It is based on the known form of propagating the Fermi hole through a canonical molecular orbital (CMO). It requires having an adequate spatial description of the relevant canonical molecular orbitals, which are obtained by expanding CMOs in terms of natural bond orbitals (NBOs). For detecting the relevant contributions of CMOs to a given Fermi contact (FC) pathway, the description of the FC in terms of the triplet polarization propagator (PP) is used. To appreciate the potential of this approach, dubbed FCCP-CMO (Fermi contact coupling pathways-CMO), it is applied to analyze the through-space transmission of the FC term of JPP SSCCs by overlap of the P lone pairs. This method can be applied using well-known quantum chemistry software without any further modification, which makes it appealing for use as a complement to SSCC measurements by NMR spectroscopy. © 2010 American Chemical Society. |
author |
Contreras, Rubén Horacio |
author_facet |
Contreras, Rubén Horacio |
author_sort |
Contreras, Rubén Horacio |
title |
Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs |
title_short |
Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs |
title_full |
Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs |
title_fullStr |
Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs |
title_full_unstemmed |
Analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. Through-space transmission by overlap of 31P lone Pairs |
title_sort |
analysis of canonical molecular orbitals to identify fermi contact coupling pathways. 1. through-space transmission by overlap of 31p lone pairs |
publishDate |
2010 |
url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v114_n2_p1044_Contreras http://hdl.handle.net/20.500.12110/paper_10895639_v114_n2_p1044_Contreras |
work_keys_str_mv |
AT contrerasrubenhoracio analysisofcanonicalmolecularorbitalstoidentifyfermicontactcouplingpathways1throughspacetransmissionbyoverlapof31plonepairs |
_version_ |
1768545295609626624 |