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Abstract Field‐stepped NMR spectroscopy at up to 36 T 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.
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This content will become publicly available on December 28, 2025
Multiple-quantum magic-angle spinning NMR spectra in the static limit: The I = 3/2 case
A simplified theoretical description of multiple-quantum excitation and mixing for nuclear magnetic resonance of half-integer quadrupolar nuclei is presented. The approach recasts the multiple-quantum nutation behavior in terms of reduced excitation and mixing curves through a scaling of the first-order offset frequency by the quadrupolar coupling constant. The two-dimensional correlation of the static first-order anisotropic line shape to the second-order anisotropic magic-angle-spinning (MAS) line shape is utilized to transform the three-dimensional integral over the three Euler angles into a single integral over the dimensionless first-order offset parameter. These transformations lead to a highly efficient algorithm for simulating the multiple-quantum (MQ)-MAS spectrum for arbitrary excitation and mixing radio frequency (RF) field strengths, pulse durations, and MAS rates within the static limit approximation, which is defined in terms of the rotation period, pulse duration, RF field strength, and quadrupolar coupling parameters. This algorithm enables a more accurate determination of the relative site populations and quadrupolar coupling parameters in a least-squares analysis of MQ-MAS spectra. Furthermore, this article examines practical considerations for eliminating experimental artifacts and employing affine transformations to improve least-squares analyses of MQ-MAS spectra. The optimum ratio of RF field strength to the quadrupolar coupling constant and the corresponding pulse durations that maximize sensitivity within experimental constraints are also examined.
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- Award ID(s):
- 2107636
- PAR ID:
- 10598353
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 161
- Issue:
- 24
- ISSN:
- 0021-9606
- Subject(s) / Keyword(s):
- Solid-state NMR quadrupolar nuclei multiple-quantum spectroscopy MAS NMR excitation and mixing optimization spectral simulation anisotropic interactions pulse sequence design NMR line shape analysis spin dynamics
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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