Structure, Chemical Bonding, and Nuclear Quadrupole Interactions of β-Cd(OH)₂:  Experiment and First Principles Calculations

Abstract

The structure of Cd(OH)(2) was determined by X-ray diffraction on powder crystals and by calculations using the full-potential linearized augmented plane wave method. Good agreement between the two results was found. The chemical bonding is characterized by the interactions of the OH(-) group with Cd(2+) which is not only electrostatic but shows some polarization or covalent admixtures and by the covalent bond in the OH(-) group. The electric field gradient (EFG) was calculated and compared with an experimental determination of the nuclear quadrupole interaction using perturbed angular correlation of gamma-rays. The calculated EFG agrees well with the EFG derived from experiment. The total electric field gradient was decomposed into contributions from different orbitals and energy regions showing that both the Cd 5p and 4d wave functions contribute significantly. Finally, the influence of spin-orbit coupling on the electric field gradient was investigated and found to be of little importance.

Biological Applications of Perturbed Angular Correlations of γ-Ray Spectroscopy

“…37 This is particularly useful in relation to calculations of EFGs because they reflect the (very) local charge distribution, as the EFG operator falls off with the cube of the distance from the PAC nucleus. For systems in the crystalline state, the density functional approach of K. Schwarz and P. Blaha 38,39 (and references therein) has provided a number of very interesting results.…”

Synthesis and Crystal Structures of Cd(OH)Cl and Cu(OH)Cl and Relationship to Brucite Type

“…The crystal structure of -Cd(OH) has been determined for the "rst time with a single crystal in 1970 (9). Very recently the structure has been revisited and the atomic position of hydrogen atom determined (10). Distances (nm) and angles (3) of the surrounding of H atom, issued from this last publication are: O}H: 0.089; (;3) O2O (acceptor): 0.324; (;3) H2O: 0.260; (;3) Cd}O}H: 118.3; (;3) O}H2O: 129.1.…”

Periodic ab initio calculation of nuclear quadrupole parameters as an assignment tool in solid-state NMR spectroscopy: applications to 23Na NMR spectra of crystalline materials

“…Full crystal, as opposed to embedded cluster methods, are generally considered to offer the best means of investigation for periodic systems [14]. Density functional theory (DFT) calculations by the full potential linearised augmented plane wave (LAPW) approach [15], for example, as implemented in the WIEN97 program [16], have resulted in good overall agreement between calculation and experiment in a range of materials with ionic character [17][18][19][20]. In particular, recent work [21] has been successful in predicting both the orientation and magnitude of the 27 Al efg tensor for the low symmetry 5-coordinate site in the mineral andalusite (Al 2 SiO 5 ) and the 49 Ti quadrupole parameters in a range of perovskite-and ilmenite-structured titanates [22].…”