Solid-state nuclear magnetic resonance (NMR) spectroscopy has long been established as offering unique atomic-scale and element-specific insight into the structure, disorder, and dynamics of materials. NMR spectra of quadrupolar nuclei (I > (1)/2) are often perceived as being challenging to acquire and to interpret because of the presence of anisotropic broadening arising from the interaction of the electric field gradient and the nuclear electric quadrupole moment, which broadens the spectral lines, often over several megahertz. Despite the vast amount of information contained in the spectral line shapes, the problems with sensitivity and resolution have, until very recently, limited the application of NMR spectroscopy of quadrupolar nuclei in the solid state. In this Perspective, we provide a brief overview of the quadrupolar interaction, describe some of the basic experimental approaches used for acquiring high-resolution NMR spectra, and discuss the information that these spectra can provide. We then describe some interesting recent examples to showcase some of the more exciting and challenging new applications of NMR spectra of quadrupolar nuclei in the fields of energy materials, microporous materials, Earth sciences, and biomaterials. Finally, we consider the possible directions that this highly informative technique may take in the future.
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http://dx.doi.org/10.1021/ja504734p | DOI Listing |
J Phys Chem A
January 2025
Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada.
We report a new NMR method for treating two-site chemical exchange involving half-integer quadrupolar nuclei in a solution. The new method was experimentally verified with extensive Na ( = 3/2), K ( = 3/2), and Rb ( = 3/2) NMR results from alkali metal ions (Na, K, and Rb) in a solution over a wide range of molecular tumbling conditions. In the fast-motion limit, all allowed single-quantum NMR transitions for a particular quadrupolar nucleus are degenerate giving rise to one Lorentzian signal.
View Article and Find Full Text PDFChem Sci
December 2024
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences Zhongshan Road 457 Dalian 116023 China
In solid-state NMR, dipolar-based heteronuclear polarization transfer has been extensively used for sensitivity enhancement and multidimensional correlations, but its efficiency often suffers from undesired spin interactions and hardware limitations. Herein, we propose a novel dipolar-echo edited R-symmetry (DEER) sequence, which is further incorporated into the INEPT-type scheme, dubbed DEER-INEPT, for achieving highly efficient heteronuclear polarization transfer. Numerical simulations and NMR experiments demonstrate that DEER-INEPT offers significantly improved robustness, enabling efficient polarization transfer under a wide range of MAS conditions, from slow to ultrafast rates, outperforming existing methods.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Department of Chemistry, Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
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.
View Article and Find Full Text PDFNano Lett
December 2024
Quantum Engineering Laboratory, Department of Electrical and Systems Engineering, University of Pennsylvania, 200 S. 33rd St., Philadelphia, Pennsylvania 19104, United States.
Nuclear quadrupolar resonance (NQR) spectroscopy reveals chemical bonding patterns in materials and molecules through the unique coupling between nuclear spins and local fields. However, traditional NQR techniques require macroscopic ensembles of nuclei to yield a detectable signal, which obscures molecule-to-molecule variations. Solid-state spin qubits, such as the nitrogen-vacancy (NV) center in diamond, facilitate the detection and control of individual nuclei through their local magnetic couplings.
View Article and Find Full Text PDFJ Phys Chem Lett
November 2024
Dept. Technische Physik II/Polymerphysik, Technische Universität Ilmenau, D-98684 Ilmenau, Germany.
The interaction of molecules, in particular, water, with solid interfaces has been studied by a multitude of methods, among them nuclear magnetic resonance spin relaxation. The frequency dependence of the relaxation times follows patterns that have been interpreted in terms of the molecular orientation and dynamics. Several different model approaches could successfully explain limiting cases of H relaxation dispersion in systems with rigid surfaces such as silica gel or glass, but none of them can reproduce the relaxation of both H and H nuclei, which differ in their respective relaxation mechanisms, dipolar vs quadrupolar.
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