We present a systematic study of the DO 22 -structure trialuminide intermetallic alloys using 27 Al NMR spectroscopy. The quadrupole splittings, Knight shifts, and spin-lattice relaxation times on Al 3 Ti, Al 3 V, Al 3 Nb, and Al 3 Ta have been identified. Knight-shift tensors were isolated by observation of quadrupole satellite lines and fitting to the central-transition powder patterns. The results are associated with the local electronic density of states for each crystallographic site. Universally small isotropic Knight shifts and long T 1 's are consistent with low Fermi-surface densities of states indicating the importance of Fermi-surface features for the phase stability of these alloys. Larger anisotropic Knight shifts occurring at aluminum site I indicate strong hybridization at this site, and the electric-field-gradient tensors confirm the strong ab plane bonding configuration. Local-moment magnetism is found in Al 3 V, yet electrically this material appears very similar to the other DO 22 aluminides. ͓S0163-1829͑98͒07112-4͔
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