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A general theory of field dependent spin-lattice relaxation for nuclei of the spin quantum number 1/2 (1H, 19F, 13C) caused by dipole-dipole interactions with neighboring quadrupolar nuclei (nuclei possessing a quadrupolar moment) is presented. The theory is valid for arbitrary motional conditions and should be treated as a quadrupolar counterpart of the paramagnetic relaxation enhancement theory. When the energy level splitting of the dipolar spin (I=1/2) matches one of the transition frequencies of the quadrupolar nuclei one can observe a local enhancement of the dipolar spin relaxation (referred to as "quadrupolar peaks"). To see such effects the dynamics modulating the spin interactions has to be relatively slow. This brings the system beyond the validity range of perturbation approaches and requires the stochastic Liouville equation to be applied. The presented theory describes the quadrupolar relaxation enhancement (QRE) for an arbitrary spin quantum number of the quadrupolar nuclei and includes the asymmetry of the quadrupolar coupling. It has been applied to interpret the shape of magnetization curves (amplitude of 1H magnetization versus magnetic field) for the molecular crystal [C3N2H5]6[Bi4Br18] ([C3N2H5]-imidazolium). The magnetization curves show several dips (local minima) attributed to 1H-14N quadrupolar relaxation enhancement effects. In addition, as a limiting case a perturbation approach to QRE has been presented and its validity conditions have been discussed.
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http://dx.doi.org/10.1016/j.ssnmr.2011.08.003 | DOI Listing |
J 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.
View Article and Find Full Text PDFSolid State Nucl Magn Reson
December 2024
Univ. Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181 - UCCS- Unité de Catalyse et de Chimie Du Solide, F-59000, Lille, France. Electronic address:
Through-space heteronuclear correlation experiments under magic-angle spinning (MAS) conditions can provide unique insights into inter-atomic proximities. In particular, it has been shown that experiments based on two consecutive coherence transfers, H → I → H, like D-HMQC (dipolar-mediated heteronuclear multiple-quantum correlation), are usually more sensitive for the indirect detection via protons of spin-3/2 quadrupolar nuclei with low gyromagnetic ratio. Nevertheless, the resolution is often decreased by the second-order quadrupolar broadening along the indirect dimension.
View Article and Find Full Text PDFWe present a comprehensive study on the best practices for integrating first principles simulations in experimental quadrupolar solid-state nuclear magnetic resonance (SS-NMR), exploiting the synergies between theory and experiment for achieving the optimal interpretation of both. Most high performance materials (HPMs), such as battery electrodes, exhibit complex SS-NMR spectra due to dynamic effects or amorphous phases. NMR crystallography for such challenging materials requires reliable, accurate, efficient computational methods for calculating NMR observables from first principles for the transfer between theoretical material structure models and the interpretation of their experimental SS-NMR spectra.
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