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- ItemMagnetic anisotropy of endohedral lanthanide ions: paramagnetic NMR study of MSc2N@C80-Ih with M running through the whole 4f row(Cambridge : RSC, 2015) Zhang, Y.; Krylov, D.; Rosenkranz, M.; Schiemenz, S.; Popov, A. A.Paramagnetic and variable temperature 13C and 45Sc nuclear magnetic resonance studies are performed for nitride clusterfullerenes MSc2N@C80 with icosahedral Ih(7) carbon cage, where M runs through all lanthanides forming nitride clusters. The influence of the endohedral lanthanide ions on the NMR spectral pattern is carefully followed, and dramatic differences are found in peak positions and line widths. Thus, 13C lines broaden from 0.01–0.02 ppm in diamagnetic MSc2N@C80 molecules (M = La, Y, Lu) to several ppm in TbSc2N@C80 and DySc2N@C80. Direction of the paramagnetic shift depends on the shape of the 4f electron density in corresponding lanthanide ions. In TmSc2N@C80 and ErSc2N@C80 with prolate 4f-density of lanthanide ions, 13C signals are shifted down-field, whereas 45Sc peaks are shifted up-field versus diamagnetic values. In all other MSc2N@C80 molecules lanthanide ions have oblate-shaped 4f electron density, and the lanthanide-induced shift is negative for 13C and positive for 45Sc peaks. Analysis of the pseudocontact and contact contributions to chemical shifts revealed that the pseudocontact term dominates both in 13C and 45Sc NMR spectra, although contact shifts for 13C signals are also considerable. Point charge computations of the ligand field splitting are performed to explain experimental results, and showed reasonable agreement with experimental pseudocontact shifts. Nitrogen atom bearing large negative charge and located close to the lanthanide ion results in large magnetic anisotropy of lanthanide ions in nitride clusterfullerenes with quasi-uniaxial ligand field.
- ItemSpin pumping at interfaces with ferro- and paramagnetic Fe60Al40films acting as spin source and spin sink(Melville, NY : American Inst. of Physics, 2022) Strusch, T.; Lenz, K.; Meckenstock, R.; Bali, R.; Ehrler, J.; Lindner, J.; Fassbender, J.; Farle, M.; Potzger, K.; Semisalova, A.We present a study of spin pumping efficiency and determine the spin mixing conductance and spin diffusion length in thin bilayer films based on 3d transition metal alloy Fe60Al40. Due to its magnetostructural phase transition, Fe60Al40 can be utilized as a ferromagnetic (FM) or paramagnetic (PM) material at the same temperature depending on its structural order; thus a thin Fe60Al40 film can act as a spin source or a spin sink when interfaced with a paramagnet or a ferromagnet, respectively. Ferromagnetic resonance measurements were performed in a frequency range of 5-35 GHz on bilayer films composed of FM-Fe60Al40/Pd and PM-Fe60Al40/Ni80Fe20 (permalloy). The increase in damping with the thickness of the paramagnetic layer was interpreted as a result of spin pumping into the paramagnet. We determine the spin mixing conductance g P d ↑↓ = (3.8 ± 0.5) × 10 18 m - 2 at the FM-Fe60Al40/Pd interface and the spin diffusion length λ P d = 9.1 ± 2.0 nm in Pd. For the PM-Fe60Al40/permalloy interface, we find a spin mixing conductance g F e A l ↑↓ = (2.1 ± 0.2) × 10 18 m - 2 and a spin diffusion length λ F e A l = 11.9 ± 0.2 nm for PM-Fe60Al40. The demonstrated bi-functionality of the Fe60Al40 alloy in spin pumping structures may be promising for spintronic applications.
- ItemHydraulic characterisation of iron-oxide-coated sand and gravel based on nuclear magnetic resonance relaxation mode analyses(Munich : EGU, 2018) Costabel, Stephan; Weidner, Christoph; Müller-Petke, Mike; Houben, GeorgThe capability of nuclear magnetic resonance (NMR) relaxometry to characterise hydraulic properties of iron-oxide-coated sand and gravel was evaluated in a laboratory study. Past studies have shown that the presence of paramagnetic iron oxides and large pores in coarse sand and gravel disturbs the otherwise linear relationship between relaxation time and pore size. Consequently, the commonly applied empirical approaches fail when deriving hydraulic quantities from NMR parameters. Recent research demonstrates that higher relaxation modes must be taken into account to relate the size of a large pore to its NMR relaxation behaviour in the presence of significant paramagnetic impurities at its pore wall. We performed NMR relaxation experiments with water-saturated natural and reworked sands and gravels, coated with natural and synthetic ferric oxides (goethite, ferrihydrite), and show that the impact of the higher relaxation modes increases significantly with increasing iron content. Since the investigated materials exhibit narrow pore size distributions, and can thus be described by a virtual bundle of capillaries with identical apparent pore radius, recently presented inversion approaches allow for estimation of a unique solution yielding the apparent capillary radius from the NMR data. We found the NMR-based apparent radii to correspond well to the effective hydraulic radii estimated from the grain size distributions of the samples for the entire range of observed iron contents. Consequently, they can be used to estimate the hydraulic conductivity using the well-known Kozeny–Carman equation without any calibration that is otherwise necessary when predicting hydraulic conductivities from NMR data. Our future research will focus on the development of relaxation time models that consider pore size distributions. Furthermore, we plan to establish a measurement system based on borehole NMR for localising iron clogging and controlling its remediation in the gravel pack of groundwater wells.