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We have performed the direct measurements of (13)C magnetic shielding for pure liquid TMS, solution of 1% TMS in CDCl3 and solid fullerene. The measurements were carried out in spherical ampoules exploring the relation between the resonance frequencies, shielding constants and magnetic moments of (13)C and (3)He nuclei. Next the (13)C shielding constants of glycine, hexamethylbenzene and adamantane were established on the basis of appropriate chemical shifts measured in the solid state. All the new results are free from susceptibility effects and can be recommended as the reference standards of (13)C shielding scale in the magic angle spinning NMR experiments.

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We present the results of gas-phase NMR measurements designed to yield a new experimental value for the absolute (1)H magnetic shielding for an isolated hydrogen molecule and its deuterium isotopomers. The results are based on the original method of direct shielding measurements (Jackowski et al., 2010) and the density dependence of (1)H, (2)H, and (3)He NMR frequencies for molecular hydrogen and atomic helium-3. The absolute isotropic magnetic shielding measured for molecular hydrogen, σ(0)(H(2)), is 26.293(5) ppm at 300 K, within experimental error of previous measurements based on spin-rotation data and quantum chemistry computations, 26.289(2) ppm (Sundholm and Gauss, 1997), and recent ab initio calculations. We also report isotope effects in shielding for H(2), HD, and D(2) molecules that are consistent with theoretical predictions. In addition, gas-phase (1)H chemical shifts extrapolated to zero density have been measured for numerous small molecules. Our results yield precise absolute shielding data that will be useful in establishing benchmark computational chemistry methods for calculating rovibrational averaged magnetic shielding.

Ab initio values of the absolute shielding constants of phosphorus and hydrogen in PH(3) were determined, and their accuracy is discussed. In particular, we analyzed the relativistic corrections to nuclear magnetic resonance (NMR) shielding constants, comparing the constants computed using the four-component Dirac-Hartree-Fock approach, the four-component density functional theory (DFT), and the Breit-Pauli perturbation theory (BPPT) with nonrelativistic Hartree-Fock or DFT reference functions. For the equilibrium geometry, we obtained σ(P) = 624.309 ppm and σ(H) = 29.761 ppm. Resonance frequencies of both nuclei were measured in gas-phase NMR experiments, and the results were extrapolated to zero density to provide the frequency ratio for an isolated PH(3) molecule. This ratio, together with the computed shielding constants, was used to determine a new value of the nuclear magnetic dipole moment of (31)P: μ(P) = 1.1309246(50) μ(N).