The Absolute Shielding Constants of Heavy Nuclei: Resolving the Enigma of the (119)Sn Absolute Shielding.
We demonstrate that the apparent disagreement between experimental determinations and four-component relativistic calculations of the absolute shielding constants of heavy nuclei is due to the breakdown of the commonly assumed relation between the electronic contribution to the nuclear spin-rotation constants and the paramagnetic contribution to the NMR shielding constants. We demonstrate that this breakdown has significant consequences for the absolute shielding constant of (119)Sn, leading to errors of about 1000 ppm. As a consequence, we expect that many absolute shielding constants of heavy nuclei will be in need of revision.
†Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Elena
E
Malkin
†Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Stanislav
S
Komorovsky
†Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Michal
M
Repisky
†Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.|‡Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.
Taye B
TB
Demissie
†Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Kenneth
K
Ruud
NMR; absolute shielding scales; nuclear magnetic moments; relativistic effects; spin-rotation constants