The nuclear magnetic resonance (NMR) spectrum of spin-3/2 nuclei in a static magnetic field aligned with one of the electric field gradient (EFG) principal axes is developed analytically, based on fictitious spin-1/2 formalism. Compact closed-form expressions for the eigenstates and transitions frequencies, as well as the expectation value of the magnetic moment after resonant excitation, are derived. Emphasis is placed on defining and interpreting the associated Rabi frequencies, as a function of excitation direction and ellipticity. It is found that transitions inherently fall into two subsets, depending on their sensitivity to excitation direction, with the Rabi frequency of one subset directly depending on the asymmetry of the EFG. A natural application is the study of Fe-based superconductors, whose antiferromagnetic ordering at low temperatures leads to a strong intrinsic magnetic field aligned with the EFG principal axes. Zero external-field NMR spectra, from powder samples of two such Fe-based superconductors, BaFe2As2 and CaFe2As2, are analyzed and exemplify the simplicity in extracting the internal magnetic field, the quadrupole coupling constant, and the EFG asymmetry parameter, which are important for studying magnetic ordering, structural properties, phase transitions, and NMR dynamics. Results compare favorably to conventional high-field NMR experiments done with the rotation of single crystals. Overall, the physical insights, afforded by the exact and concise expressions, will lead to ready interpretation of spin-3/2 spectra as well as precipitating new experimental directions.
