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 35/37Cl and 43Ca solid-state nuclear magnetic resonance (SSNMR) study of CaCl2. The 35Cl 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 CaCl2·2H2O. Chlorine-35 SSNMR spectra are also presented for CaCl2·6H2O, and when taken in concert, the SSNMR observations for CaCl2, CaCl2·2H2O, and CaCl2·6H2O 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 δiso 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 CaCl2·2H2O, and to explore the isostructural relationship between CaCl2 and CaBr2. Finally, the 43Ca CS tensor span is measured to be 31(5) ppm for anhydrous CaCl2, which represents only the fifth CS tensor span measurement for calcium.

AB INITIO CALCULATIONS OF 14N NQR PARAMETERS AND 13C, 1H, AND 15N CHEMICAL SHIFTS INCLUDING A COMPARISON WITH EXPERIMENTAL NMR DATA FOR CYCLOTRISAZOBENZENE

Nuclear quadrupole coupling constant, χ, and asymmetry parameter, η, of 14 N nucleus and 13 C , 1 H , and 15 N chemical shifts for cyclotrisazobenzene at the level of B3LYP and MP2 methods have been studied using the Gaussian 98 suite of programs. Also, nuclear quadrupole resonance (NQR) frequencies (ν0, ν+, ν-) for 14 N have been calculated, thoroughly. The optimized structure of the compound was very similar to that given by the X-ray crystallographic data. The electric field gradient (EFG) calculation verified that the N = N bonds are highly localized in this molecule; therefore, electron-pairs of the nitrogen atoms remain nonbonding. The comparison of the calculated chemical shifts with the experimental values for cyclotrisazobenzene shows no significant structural changes in solution.

The Nuclear Quadrupole Moment of 14N from Accurate Electric Field Gradient Calculations and Microwave Spectra of NP Molecule

Extensive series of relativistic coupled cluster calculations of the electric field gradient at N in NP has been carried out. The accurate value of the calculated electric field gradient, combined with the highly accurate experimental value of the nuclear quadrupole coupling constant for the 14N nucleus, gives the 'molecular' value of the nuclear quadrupole moment Q(14N) = 20.46 mb. This result perfectly agrees with the value (20.44 ± 0.03 mb) determined from atomic calculations and atomic spectra. The present study involves also extensive investigations of basis sets which must be used in highly accurate calculations of electric field gradients.

Distribution of Electric Field Gradient at Aluminum Sites in Zeolite Loaded with Potassium

In the zeolite LTA, loaded with potassium, the temperature and field dependence of 27Al NQR was observed. Symmetrical single shoulders are found on both sides of the central line. The shape and the shift of those shoulders show no dependence on both temperature and the strength of the external field. This evidences a first order electric quadrupolar shift, being the result of the distribution of the nuclear quadrupole coupling constant and the asymmetry parameter at 27Al sites