Exact calculation, using angular momentum, of combined Zeeman and quadrupolar interactions in NMR

The NMR of nuclei with spins greater than 1/2 is often strongly influenced by the quadrupole interaction. This combination of Zeeman and quadrupole terms can usually be treated using perturbation theory, but an exact calculation is also needed. We explain an exact approach that eliminates the evaluation of commutators of complicated operators. Instead, the calculation is based on matrix elements of the Liouvillian, the commutator with the Hamiltonian. The spectrum can then be calculated directly from the eigenvectors and eigenvalues of the Liouvillian. With the aid of angular momentum methods, it can be shown that the quadupole interaction for spin I is fully determined by only (2 I -1) reduced matrix elements--for spin 3/2, this means only two quantities. The exact nature of the various basis operators is not needed, since the calculation only needs the angular momentum quantum numbers. The full Liouvillian matrix can be calculated from selection rules and the Wigner-Eckart theorem. Furthermore, we present an expression for these reduced matrix elements which is valid for any spin. This theory covers the whole range from quadrupole-perturbed NMR spectra to Zeeman-perturbed nuclear quadrupole resonance.