Quadrupole coupling structures

Quadrupole coupling constants for molecules are usually determined from the hyperfine structure of pure rotational spectra or from electric-beam and magnetic-beam resonance spectroscopies. Nuclear magnetic resonance, electron spin resonance and Mossbauer spectroscopies are also routes to the property. There is a large amount of experimental data for and halogen-substituted molecules. Less data is available for deuterium because the nuclear quadrupole is small. 

W(VI) compounds with 5cP electronic configuration, the EFG is reasonably weU described by the lattice contribution only. The regular octahedral WOs structure yields zero EFG in agreement with experiment, while the deformed tetrahedral W04 strucmre results in significant quadrupole coupling constants of either sign, e Q > 0 and also <0, depending on the distortion of the O4 tetrahedron. 

The spectra discussed in Chapter 4 were analyzed by neglecting the effects of nuclear quadrupole coupling on the nuclear hyperfine structure. Presented here is the way such effects may be incorporated into the spectra using perturbation theory. 

Numerous X-ray investigations have unravelled the solid state structure of contact and solvent-separated ion pairs. It was therefore considered to be of interest to evaluate also the potential of solid state NMR as a tool for the investigation of this structural problem. In addition to the study of chemical shifts discussed above (Section II.B), the quadrupole coupling constant of the nuclide Li, x( Li), was expected to be an ideal sensor for the bonding situation around the lithium cation because, due to its dependence on the electric field gradient, the quadrupolar interaction for this spin-3/2 nucleus is strongly influenced by local symmetry, as exemplified in Section II.C.3. This is also shown with some model calculations in Section ILF. 

The microwave spectra of 1//-benzotriazole and its N-D isotopomer have been studied in a heated cell. The molecule is planar. Due to the quadrupole coupling effects of the N nuclei, no hyperfine structures are observed. The dipole moment of benzotriazole obtained by microwave is 4.3 D, which is in agreement with the value determined in solution. The rotational spectrum is also assigned <93JSP(161)136>. 

A 3H and 2H NMR study of single crystals of [Ag(NH3)2][Ag(ONO)2] has been reported.32 Rapid reorientational motions of the ammine groups around their C3 axes were found. The orientations of the C3 axes within the crystal corresponded with the Ag—N bond directions of the [H3N—Ag—NH3]+ unit. The deuterium quadrupole coupling constant was determined and found to be identical to that of solid ND3. It was concluded that the electronic configuration and the geometric structure of ammonia were changed only very slightly upon coordination to silver ions. 

---