Theoretical study of homonuclear J coupling between quadrupolar spins: Single-crystal, DOR, and J-resolved NMR

Abstract

The theory describing homonuclear indirect nuclear spin–spin coupling (J) interactions between pairs of quadrupolar nuclei is outlined and supported by numerical calculations. The expected first-order multiplets for pairs of magnetically equivalent (A2), chemically equivalent (AA′), and non-equivalent (AX) quadrupolar nuclei are given. The various spectral changeovers from one first-order multiplet to another are investigated with numerical simulations using the SIMPSON program and the various thresholds defining each situation are given. The effects of chemical equivalence, as well as quadrupolar coupling, chemical shift differences, and dipolar coupling on double-rotation (DOR) and J-resolved NMR experiments for measuring homonuclear J coupling constants are investigated. The simulated J coupling multiplets under DOR conditions largely resemble the ideal multiplets predicted for single crystals, and a characteristic multiplet is expected for each of the A2, AA′, and AX cases. The simulations demonstrate that it should be straightforward to distinguish between magnetic inequivalence and equivalence using J-resolved NMR, as was speculated previously. Additionally, it is shown that the second-order quadrupolar-dipolar cross-term does not affect the splittings in J-resolved experiments. Overall, the homonuclear J-resolved experiment for half-integer quadrupolar nuclei is demonstrated to be robust with respect to the effects of first- and second-order quadrupolar coupling, dipolar coupling, and chemical shift differences.