Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings
The second-rank tensor character of the paramagnetic spin-orbit and spin-dipolar contributions to nuclear spin-spin coupling constants is usually ignored when NMR measurements are carried out in the isotropic phase. However, in this study it is shown that isotropic 2J FF couplings strongly depend on...
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2012
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v116_n20_p4930_Ducati http://hdl.handle.net/20.500.12110/paper_10895639_v116_n20_p4930_Ducati |
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paper:paper_10895639_v116_n20_p4930_Ducati2023-06-08T16:06:31Z Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings Ab initio C-F bonds Geometrical effect Isotropic phase Model system NMR measurements Nuclear magnetic shieldings Qualitative approach Relative orientation Spin orbits Spin-spin coupling constants Spin-spin couplings Calculations Couplings Magnetic shielding Paramagnetism Tensors Electron spin resonance spectroscopy carbon fluorine article chemistry nuclear magnetic resonance spectroscopy quantum theory standard Carbon Fluorine Magnetic Resonance Spectroscopy Quantum Theory Reference Standards The second-rank tensor character of the paramagnetic spin-orbit and spin-dipolar contributions to nuclear spin-spin coupling constants is usually ignored when NMR measurements are carried out in the isotropic phase. However, in this study it is shown that isotropic 2J FF couplings strongly depend on the relative orientation of the C-F bonds containing the coupling nuclei and the eigenvectors of such tensors. Predictions about such effect are obtained using a qualitative approach based on the polarization propagator formalism at the RPA, and results are corroborated performing high-level ab initio spin-spin coupling calculations at the SOPPA(CCSD)/EPR-III/ /MP2/EPR-III level in a model system. It is highlighted that no calculations at the RPA level were carried out in this work. The quite promising results reported in this paper suggest that similar properties are expected to hold for the second-rank nuclear magnetic shielding tensor. © 2012 American Chemical Society. 2012 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v116_n20_p4930_Ducati http://hdl.handle.net/20.500.12110/paper_10895639_v116_n20_p4930_Ducati |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Ab initio C-F bonds Geometrical effect Isotropic phase Model system NMR measurements Nuclear magnetic shieldings Qualitative approach Relative orientation Spin orbits Spin-spin coupling constants Spin-spin couplings Calculations Couplings Magnetic shielding Paramagnetism Tensors Electron spin resonance spectroscopy carbon fluorine article chemistry nuclear magnetic resonance spectroscopy quantum theory standard Carbon Fluorine Magnetic Resonance Spectroscopy Quantum Theory Reference Standards |
| spellingShingle |
Ab initio C-F bonds Geometrical effect Isotropic phase Model system NMR measurements Nuclear magnetic shieldings Qualitative approach Relative orientation Spin orbits Spin-spin coupling constants Spin-spin couplings Calculations Couplings Magnetic shielding Paramagnetism Tensors Electron spin resonance spectroscopy carbon fluorine article chemistry nuclear magnetic resonance spectroscopy quantum theory standard Carbon Fluorine Magnetic Resonance Spectroscopy Quantum Theory Reference Standards Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings |
| topic_facet |
Ab initio C-F bonds Geometrical effect Isotropic phase Model system NMR measurements Nuclear magnetic shieldings Qualitative approach Relative orientation Spin orbits Spin-spin coupling constants Spin-spin couplings Calculations Couplings Magnetic shielding Paramagnetism Tensors Electron spin resonance spectroscopy carbon fluorine article chemistry nuclear magnetic resonance spectroscopy quantum theory standard Carbon Fluorine Magnetic Resonance Spectroscopy Quantum Theory Reference Standards |
| description |
The second-rank tensor character of the paramagnetic spin-orbit and spin-dipolar contributions to nuclear spin-spin coupling constants is usually ignored when NMR measurements are carried out in the isotropic phase. However, in this study it is shown that isotropic 2J FF couplings strongly depend on the relative orientation of the C-F bonds containing the coupling nuclei and the eigenvectors of such tensors. Predictions about such effect are obtained using a qualitative approach based on the polarization propagator formalism at the RPA, and results are corroborated performing high-level ab initio spin-spin coupling calculations at the SOPPA(CCSD)/EPR-III/ /MP2/EPR-III level in a model system. It is highlighted that no calculations at the RPA level were carried out in this work. The quite promising results reported in this paper suggest that similar properties are expected to hold for the second-rank nuclear magnetic shielding tensor. © 2012 American Chemical Society. |
| title |
Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings |
| title_short |
Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings |
| title_full |
Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings |
| title_fullStr |
Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings |
| title_full_unstemmed |
Unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 J FF couplings |
| title_sort |
unexpected geometrical effects on paramagnetic spin-orbit and spin-dipolar 2 j ff couplings |
| publishDate |
2012 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v116_n20_p4930_Ducati http://hdl.handle.net/20.500.12110/paper_10895639_v116_n20_p4930_Ducati |
| _version_ |
1768545201935089664 |