The quadrupolar and chemical shift tensors, as well as the relative orientation of the two principle axis systems, are accurately determined using a two‐dimensional nuclear magnetic resonance technique. Good agreement between experimental and simulated two‐dimensional spectra is obtained for a series of rubidium and sodium compounds at multiple magnetic field strengths. Extension of this technique to correlate the quadrupolar and dipolar interactions, as well as the incorporation of a purely isotropic dimension resulting in a three‐dimensional experiment is also discussed.

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