Field-stepped ultra-wideline NMR at up to 36T: On the inequivalence between field and frequency stepping.

Abstract

Field-stepped NMR spectroscopy at up to 36T using the series-connected hybrid (SCH) magnet at the U.S. National High Magnetic Field Laboratory is demonstrated for acquiring ultra-wideline powder spectra of nuclei with very large quadrupolar interactions. Historically, NMR evolved from the continuous-wave (cw) field-swept method in the early days to the pulsed Fourier-transform method in the modern era. Spectra acquired using field sweeping are generally considered to be equivalent to those acquired using the pulsed method. Here, it is shown that field-stepped wideline spectra of half-integer spin quadrupolar nuclei acquired using WURST/CPMG methods can be significantly different from those acquired with the frequency-stepped method commonly used with superconducting magnets. The inequivalence arises from magnetic field-dependent NMR interactions such as the anisotropic chemical shift and second-order quadrupolar interactions; the latter is often the main interaction leading to ultra-wideline powder patterns of half-integer spin quadrupolar nuclei. This inequivalence needs be taken into account to accurately and correctly determine the quadrupolar coupling and chemical shift parameters. A simulation protocol is developed for spectral fitting to facilitate analysis of field-stepped ultra-wideline NMR spectra acquired using powered magnets. A MATLAB program which implements this protocol is available on request.