Role of Spin-Dependent Terms in the Relationship among Nuclear Spin-Rotation and NMR Magnetic Shielding Tensors

I. A. AUCAR,; S. S. GÓMEZ; C. G. GIRIBET; G.A. AUCAR

The Journal of Physical Chemical Letters

AMER CHEMICAL SOC

Lugar: Washington; Año: 2016 vol. 7 p. 5188 - 5192

1948-7185

The broadly accepted procedure to obtain the experimentalabsolute scale of NMR magnetic shieldings, σ, is well-known for nonheavyatom-containing molecules. It was uncovered more than 40 years ago by the worksof Ramsey and Flygare. They found a quite accurate relationship among σ and thenuclear spin-rotation constants. Its relativistic extension was very recentlyproposed, although it has an intrinsic weakness because a new SO-S twocomponentterm needs to be considered. We show how to overcome thisproblem. We found that (νYS − νYatom,S) generalizes the SO-S term, where νYS =⟨⟨[((r − rY) × α)/(|r − rY|3)]; S(4)⟩⟩, 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.