Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings

In this chapter, several nJXY SSCC trends involving the X and Y light atoms are discussed with considerable detail for different values of n, the number of formal bonds separating both coupling nuclei. First, couplings contributed mainly by the FC interaction are considered. Insight into their trans...

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Autores principales: Contreras, R.H., Tormena, C.F., Ducati, L.C.
Formato: SER
Materias:
FC transmission
Geometric effect
Multipath transmission
Perlin effect
PSO transmission
Qualitative model
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_18754023_v3_n1_p245_Contreras
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_18754023_v3_n1_p245_Contreras
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spelling todo:paper_18754023_v3_n1_p245_Contreras2023-10-03T16:34:13Z Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings Contreras, R.H. Tormena, C.F. Ducati, L.C. FC transmission Geometric effect Multipath transmission Perlin effect PSO transmission Qualitative model In this chapter, several nJXY SSCC trends involving the X and Y light atoms are discussed with considerable detail for different values of n, the number of formal bonds separating both coupling nuclei. First, couplings contributed mainly by the FC interaction are considered. Insight into their transmission mechanisms is obtained using at least one of the following three approaches: (a) the qualitative model described in Chapter 2; (b) the FCCP-CMO approach, that is, studying Fermi contact coupling pathways in terms of canonical molecular orbitals; and (c) by using explicitly the known connection between the Fermi Hole and the FC term transmissions. Among others, the following interesting examples are mentioned, the "Perlin effect" for n=1 and X=C and Y=either C or H. The different signs known experimentally for analogous geminal couplings are discussed in terms of exchange interactions taking place in the region where both bonds overlap. For multicyclic compounds with n= 4, the FC transmission between bridgehead carbon atoms is rationalized in terms of series of concatenated sequences of hyperconjugative interactions involving those bridgehead atoms. Although the main emphasis is put on the FC term for different SSCCs, some discussions include also "noncontact" terms, where the PSO and DSO terms are described in some detail. In some cases, they are discussed in terms of the qualitative model described in Chapter 2, and examples where the "geometric effect" can be envisaged on physical grounds are described. This is only a brief description of some of the many interesting examples discussed within this chapter. © 2013 Elsevier B.V. SER info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_18754023_v3_n1_p245_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 FC transmission
Geometric effect
Multipath transmission
Perlin effect
PSO transmission
Qualitative model
spellingShingle FC transmission
Geometric effect
Multipath transmission
Perlin effect
PSO transmission
Qualitative model
Contreras, R.H.
Tormena, C.F.
Ducati, L.C.
Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings
topic_facet FC transmission
Geometric effect
Multipath transmission
Perlin effect
PSO transmission
Qualitative model
description In this chapter, several nJXY SSCC trends involving the X and Y light atoms are discussed with considerable detail for different values of n, the number of formal bonds separating both coupling nuclei. First, couplings contributed mainly by the FC interaction are considered. Insight into their transmission mechanisms is obtained using at least one of the following three approaches: (a) the qualitative model described in Chapter 2; (b) the FCCP-CMO approach, that is, studying Fermi contact coupling pathways in terms of canonical molecular orbitals; and (c) by using explicitly the known connection between the Fermi Hole and the FC term transmissions. Among others, the following interesting examples are mentioned, the "Perlin effect" for n=1 and X=C and Y=either C or H. The different signs known experimentally for analogous geminal couplings are discussed in terms of exchange interactions taking place in the region where both bonds overlap. For multicyclic compounds with n= 4, the FC transmission between bridgehead carbon atoms is rationalized in terms of series of concatenated sequences of hyperconjugative interactions involving those bridgehead atoms. Although the main emphasis is put on the FC term for different SSCCs, some discussions include also "noncontact" terms, where the PSO and DSO terms are described in some detail. In some cases, they are discussed in terms of the qualitative model described in Chapter 2, and examples where the "geometric effect" can be envisaged on physical grounds are described. This is only a brief description of some of the many interesting examples discussed within this chapter. © 2013 Elsevier B.V.
format SER
author Contreras, R.H.
Tormena, C.F.
Ducati, L.C.
author_facet Contreras, R.H.
Tormena, C.F.
Ducati, L.C.
author_sort Contreras, R.H.
title Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings
title_short Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings
title_full Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings
title_fullStr Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings
title_full_unstemmed Transmission Mechanisms of the Fermi-Contact Term of Spin-Spin Couplings
title_sort transmission mechanisms of the fermi-contact term of spin-spin couplings
url http://hdl.handle.net/20.500.12110/paper_18754023_v3_n1_p245_Contreras
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