Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds
The nuclear magnetic shieldings of Si, Ge, and Sn in MH4−nYn (M = Si, Ge, Sn; Y = F, Cl, Br, I and n = 1–4) molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to...
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2014
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paper:paper_16102940_v20_n9_p_Maldonado2023-06-08T16:25:06Z Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds Aucar, Gustavo A. Melo, Juan Ignacio LRESC NMR Polarization propagators Relativistic effects germanium halogen hydrogen iodine lead ligand proton silicon tin Article atom electron excitation magnetic field magnetism nuclear magnetic resonance spectroscopy polarization proton nuclear magnetic resonance The nuclear magnetic shieldings of Si, Ge, and Sn in MH4−nYn (M = Si, Ge, Sn; Y = F, Cl, Br, I and n = 1–4) molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the “heavy atom effect on vicinal heavy atom” (HAVHA), in more detail. We found that the main electronic mechanism is the spin–orbit or σp T(3) correction, although other corrections such as σp S(1) and σp S(3) are also important. Finally, we analyzed proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine. © 2014, Springer-Verlag Berlin Heidelberg. Fil:Aucar, G.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Melo, J.I. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_16102940_v20_n9_p_Maldonado http://hdl.handle.net/20.500.12110/paper_16102940_v20_n9_p_Maldonado |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
LRESC NMR Polarization propagators Relativistic effects germanium halogen hydrogen iodine lead ligand proton silicon tin Article atom electron excitation magnetic field magnetism nuclear magnetic resonance spectroscopy polarization proton nuclear magnetic resonance |
| spellingShingle |
LRESC NMR Polarization propagators Relativistic effects germanium halogen hydrogen iodine lead ligand proton silicon tin Article atom electron excitation magnetic field magnetism nuclear magnetic resonance spectroscopy polarization proton nuclear magnetic resonance Aucar, Gustavo A. Melo, Juan Ignacio Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds |
| topic_facet |
LRESC NMR Polarization propagators Relativistic effects germanium halogen hydrogen iodine lead ligand proton silicon tin Article atom electron excitation magnetic field magnetism nuclear magnetic resonance spectroscopy polarization proton nuclear magnetic resonance |
| description |
The nuclear magnetic shieldings of Si, Ge, and Sn in MH4−nYn (M = Si, Ge, Sn; Y = F, Cl, Br, I and n = 1–4) molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the “heavy atom effect on vicinal heavy atom” (HAVHA), in more detail. We found that the main electronic mechanism is the spin–orbit or σp T(3) correction, although other corrections such as σp S(1) and σp S(3) are also important. Finally, we analyzed proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine. © 2014, Springer-Verlag Berlin Heidelberg. |
| author |
Aucar, Gustavo A. Melo, Juan Ignacio |
| author_facet |
Aucar, Gustavo A. Melo, Juan Ignacio |
| author_sort |
Aucar, Gustavo A. |
| title |
Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds |
| title_short |
Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds |
| title_full |
Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds |
| title_fullStr |
Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds |
| title_full_unstemmed |
Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds |
| title_sort |
core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in mh4−nyn (n = 0–4; m = si, ge, sn, and y = h, f, cl, br, i) model compounds |
| publishDate |
2014 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_16102940_v20_n9_p_Maldonado http://hdl.handle.net/20.500.12110/paper_16102940_v20_n9_p_Maldonado |
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| _version_ |
1768542522878984192 |