INVESTIGADORES
AUCAR Ignacio Agustin
artículos
Título:
Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors
Autor/es:
AUCAR, IGNACIO AGUSTÍN; GOMEZ, SERGIO SANTIAGO; GIRIBET, CLAUDIA GLORIA; AUCAR, GUSTAVO ADOLFO
Revista:
The Journal of Physical Chemistry Letters
Editorial:
American Chemical Society
Referencias:
Lugar: Washington; Año: 2016 vol. 7 p. 5188 - 5192
Resumen:
The broadly accepted procedure to obtain the experimental absolute scale of NMR magnetic shieldings, σ, is well-known for nonheavy atom-containing molecules. It was uncovered more than 40 years ago by the works of Ramsey and Flygare. They found a quite accurate relationship among σ and the nuclear spin-rotation constants. Its relativistic extension was very recently proposed, although it has an intrinsic weakness because a new SO-S two-component term needs to be considered. We show how to overcome this problem. We found that (νS − νatom,S) generalizes the SO-S term, where νS = ⟨⟨[((r − rY) × α)/(|r − rY| )]; S ⟩⟩, r − rY is the electron position with respect to the position of nucleus Y, and S(4) is the four-component total electron spin. When including this new term, one finds that the best of our relativistic Flygare-like models fits quite well with the results of the most accurate method available at the moment. We also show that the difference among the parallel component of σ(Xe) in XeF2 and σ(Xe) of the free atom is almost completely described by thatnew term.