Quadrupolar nuclei linewidths

A further factor to be taken into account when assessing the relative ease with which a quadrupolar nucleus may be observed is the width of the line which is determined for a given electric field gradient by the quadrupole moment (also listed in Table 1.2). Often only the central transition is observed, for which the linewidth is determined by its second-order quadrupolar broadening and is proportional to [Q (I(I +... 

Since the short relaxation times associated with a quadrupolar nucleus drastically reduce the time delay to be applied in an NMR experiment between two pulses, measuring times are short or, in other words, distinct NMR signals can often be detected with a limited time spent down to micromolar concentrations. Along with this apparent advantage, quadrupolar nuclei provide information in addition to the classical parameters chemical shift (or shielding) and nuclear spin-spin coupling constants. Variations in linewidths for quadrupolar nuclei are another sensitive quantity allowing for the evaluation of the electronic and the steric situation in the first coordination sphere of a vanadium compound, its periphery, its (local) symmetry and its interaction with the matrix, i.e. counter-ions, solvent molecules and other constituents present in solution. 

The relaxation rates of a quadrupolar nucleus are dictated by two new factors not previously considered. The first is the magnitude of the quadrupole moment itself (Table 2.3). Larger values contribute to more efficient spin relaxation and hence broader linewidths, whereas smaller values typically produce sharper lines. Thus, those nuclei with smaller quadrupole moments are usually more favoured for NMR observation. As before, for the mechanism to be effective, molecular tumbling must occur at an appropriate... 

The resonances of a quadrupolar nucleus itself are also broad if its relaxation time is very short. The linewidths themselves may give useful chemical information, but obviously very broad bands will not show... 

Some appreciation for the nitrogen nuclear characteristics may be obtained from Table 1. Because the relative sensitivities are comparable, the approximately 300-fold higher natural abundance of would seem to make it the nucleus of choice. It is even more sensitive than at natural abundance. However, like all nuclei with spin quantum number I > 1/2, possesses an electric quadrupole moment that arises from a nonspherical electric charge distribution in the nucleus itself. When placed in an electric field gradient, such as that characteristic of most molecular electron distributions, a quadrupolar nucleus experiences random fluctuating electric fields. The characteristic frequencies of these motions have components at the resonance frequency and hence afford an efficient relaxation mechanism. As a result, spin-lattice relaxation times (Tj ) are very short, 0.1-10 ms. Because Tj = To for in most molecules Lie in solution, linewidths are corres-... 

For a quadrupolar nucleus in a rapidly tumbling molecule, Tj may often be directly deduced from the linewidth. Even so, it may be advisable to check with a direct measurement made as above, provided that such a measurement is not vitiated by interference from magnetization components normal to the field which have not... 

Much more important for observation of the metal nuclei is the scalar coupling contribution to Tf, which decreases steadily with decreasing Tf of the quadrupolar nucleus. Table 1 indicates the linewidths caused when 7 is 10 s and J is 1000 Hz... 

The isotropic g and a values are now replaced by two 3x3 matrices representing the g and A tensors and which arise from the anisotropic electron Zeeman and hyperfine interaction. Other energy terms may also be included in the spin Hamiltonian, including the anisotropic fine term D, for electron-electron interactions, and the anisotropic nuclear quadrupolar interaction Q, depending on the nucleus. Usually the quadrupolar interachons are very small, compared to A and D, are generally less than the inherent linewidth of the EPR signal and are therefore invisible by EPR. They are readily detected in hyperfine techniques such as ENDOR and HYSCORE. All these terms (g. A, D) are anisotropic in the solid state, and must therefore be defined in terms of a tensor, which will be explained in this section. 

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