A multinuclear solid-state magnetic resonance and GIPAW DFT study of anhydrous calcium chloride and its hydrates

The group 2 metal halides and corresponding metal halide hydrates serve as useful model systems for understanding the relationship between the electric field gradient (EFG) and chemical shift (CS) tensors at the halogen nuclei and the local molecular and electronic structure. Here, we present a 35/37 Cl and 43 Ca solid-state nuclear magnetic resonance (SSNMR) study of CaCl 2 . The 35 Cl nuclear quadrupole coupling constant, 8.82(8) MHz, and the isotropic chlorine CS, 105(8) ppm (with respect to dilute NaCl(aq)), are different from the values reported previously for this compound, as well as those reported for CaCl 2 ·2H 2 O. Chlorine-35 SSNMR spectra are also presented for CaCl 2 ·6H 2 O, and when taken in concert, the SSNMR observations for CaCl 2 , CaCl 2 ·2H 2 O, and CaCl 2 ·6H 2 O clearly demonstrate the sensitivity of the chlorine EFG and CS tensors to the local symmetry and to changes in the hydration state. For example, the value of δ iso decreases with increasing hydration. Gauge-including projector-augmented wave (GIPAW) density functional theory (DFT) calculations are used to substantiate the experimental SSNMR findings, to rule out the presence of other hydrates in our samples, to refine the hydrogen positions in CaCl 2 ·2H 2 O, and to explore the isostructural relationship between CaCl 2 and CaBr 2 . Finally, the 43 Ca CS tensor span is measured to be 31(5) ppm for anhydrous CaCl 2 , which represents only the fifth CS tensor span measurement for calcium.