New Experimental NMR Shielding Scales Mapped Relativistically from NSR: Theory and Application

Abstract

The recently proposed relativistic mapping between nuclear magnetic resonance (NMR) shielding and nuclear spin-rotation (NSR) coupling tensors [J. Chem. Phys. 2013, 138, 134104] is employed to establish new experimental (more precisely, experimentally derived) absolute shielding constants for H and X in HX (X = F, Cl, Br, and I). The results are much more accurate than the old "experimental" values that were based on the well-known nonrelativistic mapping. The relativistic mapping is very robust in the sense that it is rather insensitive to the quality of one-particle basis sets and the treatment of electron correlation. Relativistic effects in the NSR coupling constants are also elucidated in depth.