Influence of size effects on the Knight shift of NMR lines in the gallium-indium alloy

A study is reported of the Knight shift of ⁷¹Ga, ⁶⁹Ga, and ¹¹⁵In NMR lines in a liquid gallium-indium alloy with a composition of 90 at % Ga and 10 at % In, introduced into porous glasses with pore sizes of 5 and 200 nm, relative to the corresponding shifts in the bulk alloy. The measurements have been performed at room temperature. The study has revealed a size-dependent decrease in the Knight shift. A sample with a 5-nm pore size has demonstrated a noticeable difference in the magnitudes of the Knight shift of both gallium isotopes measured in magnetic fields of 9.4 and 17.6 T, which implies a dependence of the electronic susceptibility of the melt on the magnetic field under the nanoconfinement conditions.     

NMR Knight shift studies in SmSn3 — Extension to low temperatures

The ¹¹⁹Sn Knight shift in SmSn3 has been measured in the temperature range 15—300 K, and it is found that the 4f-contribution to the Knight shift does not show a sign reversal in this temperature interval. The range of crystal field parameters for which simultaneous fit to the magnetic susceptibility and the extended Knight shift results in SmSn3 is obtained can be substantially narrowed from that reported earlier.     

NMR probe of bulk electronic structures in H+ beam irradiated Bi2Te3 topological insulator

We report a nuclear magnetic resonance (NMR) study on H⁺ beam irradiated Bi₂Te₃ powdered single crystals. In this work, we demonstrate that the beam creates defects within its penetration range giving rise to delocalized charge carriers, thereby making further ¹²⁵Te NMR Knight shift and line broadening. Upon increasing temperature, the NMR line narrowing manifests the activated motions of thermally excited charge carriers in the irradiated sample. In contrast, it reveals that in the unirradiated sample the free-charge carriers at the Fermi level dominantly contribute to the Knight shift. Our results show that the orbital contribution to the Knight shift in the bulk state of Bi₂Te₃ becomes predominant in the system with the higher density of defects, as evidenced by modified electronic structures induced by the beam irradiation.     

<Superscript>2</Superscript>H and <Superscript>47, 49</Superscript>Ti nuclear magnetic resonance in the γ phase of titanium deuterides TiD<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Titanium deuterides TiD_1.92, TiD_1.98, and TiD_2.0 have been studied by ²H and ^{47, 49}Ti NMR in a magnetic field of 7.04 T and a temperature range of 120–500 K. At all temperatures and compositions, the ²H NMR line is a singlet described by the Gaussian function. The contribution of demagnetizing fields to the ²H NMR shift is ∼50 ppm. The titanium NMR spectra for all compositions comprise two signals due to the ⁴⁷Ti and ⁴⁹Ti isotopes. The shift between these signals depends on the deuterium content and temperature. The ^{47, 49}Ti NMR line shape, width, and shifts have been considered in the framework of second-order quadrupole effects for a tetragonal lattice distortion and random distribution of vacancies. The Knight shifts σ(²H) and K(^{47, 49}Ti) are a function of temperature with a clearly pronounced singularity at ∼300 K. The contact, orbital, and polarization contributions to the Knight shifts have been estimated from analysis of the temperature dependences of σ(²H) and K(^{47, 49}Ti).     

NMR of mercury in porous carbon and silica gel

The temperature dependences of the integrated intensity and of the Knight shift of ¹⁹⁹Hg NMR signals are measured for liquid and solid mercury introduced into porous carbon and silica gel. A decrease in the temperature of completion of crystallization and a small temperature hysteresis (from 4 to 9 K) between melting and crystallization are observed. The melting temperature of mercury in pores coincides with that in the bulk. The ¹⁹⁹Hg NMR signal from crystalline mercury under the condition of restricted geometry is observed for the first time. It is established that the Knight shift for liquid and crystalline mercury in pores is smaller than in the bulk.     

NMR studies of single crystals of the topological insulator Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> at low temperatures

A powder sample and single-crystal plates of the topological insulator Bi₂Te₃ have been investigated using the ¹²⁵Te NMR method at room temperature and at low temperatures in the range from 12.5 to 16.5 K. The NMR spectra of the single-crystal plates have been studied in the orientation where the crystallographic axis c is directed parallel or perpendicular to the magnetic field. The spectra have been obtained by means of recording spin-echo signals and plotting their envelopes. It has been shown that the NMR spectra for the bismuth telluride powder and plates with the orientation c ⊥ B consist of two lines, which are presumably attributed to tellurium nuclei in two crystallographic positions in the bulk of the sample. The position and shape of the lines are determined by the chemical shift and the Knight shift. For the orientation of the plates c || B, the spectrum contains an additional component in the high-frequency region, which cannot appear due to the angular dependence of the line shifts caused by tellurium nuclei in the bulk of the topological insulator. At a low temperature, the additional line dominates in the spectrum.     

Temperature dependence of the positive-muon knight shift in MnSi

The temperature dependence of the μ⁺ Knight shift in weakly-helimagnetic MnSi has been measured in the temperature range between 28 and 300 K. The observed shift is found to be directly proportional to the host susceptibility in the paramagnetic state with a hyperfine coupling constant of —4.8 kOe/_μB.     

93Nb knight shift and quadrupole coupling parameters in the orthorhombic β phase hydride and deuteride of niobium

The Knight shift tensor components and quadrupole coupling parameters of the ⁹³Nb NMR have been measured for the first time in the orthorhombic β phase hydride and deuteride of niobium. The isotropic component of the Knight shift tensor has the same value in the hydride phase as in the solid solution (α') phase at the same composition, indicating that no significant change in band structure details occurs as a consequence of the structural phase transition. Comparison of the measured asymmetry parameter of the quadrupole interaction with calculated values indicates that the probable Nb environment is that of the ordered NbH structure. Estimates of the activation energy for hydrogen (deuterium) diffusion are obtained from the temperature dependence of the linewidths of the spectrum features.     

Controversy about the reference compound for correct chemical shift determination of 195Pt nuclei

Several groups exploring the ¹⁹⁵Pt NMR in solids, including metallic and magnetic materials, use different standards for chemical shift (Knight shift) determination. Commonly applied H₂PtCl₆ and Na₂PtCl₆ (IUPAC δ scale) lead to considerable underestimation of the shifts since H₂PtCl₆ has considerable own ¹⁹⁵Pt NMR shift due to its Van Vleck paramagnetism. In this Letter new results on ¹⁹⁵Pt NMR in heavy fermion system CeInPt₄ are presented and rationalized scale for the Knight shift determination is discussed.     

NMR study of topological insulator Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> in a wide temperature range

NMR studies of ¹²⁵Te in the topological insulator bismuth telluride Bi₂Te₃ in a wide temperature range from room temperature to 12.5 K are performed. The pulsed NMR spectrometer Bruker Avance 400 is applied. The NMR spectra are obtained for the powder from Bi2Te3 single crystal and monocrystalline plates with the orientations c || B and c ⊥ B. At room temperature, the spectra consist of two lines related to two nonequivalent positions of tellurium nuclei Te1 and Te2. The parameters of the NMR frequency shift tensor are found from the powder spectrum. The temperature dependences of the spectra for the powder and plates with the orientation c ⊥ B agree with each other. The line shift with decreasing temperature is explained by the reduction of the Knight shift. The thermal activation energy of charge carriers is estimated. The spectra for the plates with the orientation c || B demonstrate peculiar behavior below 91 K. The spin-lattice relaxation time for the powder and monocrystalline plates with both orientations at room temperature is measured.     

31P NMR Knight shifts in the UPY(Y = S,Se, Te) compounds

Nuclear magnetic resonance of ³¹P measurements have been made for UPY (where Y = S, Se and Te) compounds. The resonane lines show the effect of anisotropic Knight shifts. In the UPS, the NMR data indicate an axial symmetry of the phosphorus environment whereas for UPSe and UPTe the symmetry is lower than the axial one. The result for UPSe disagrees with earlier structural studies. An analysis of NMR spectra indicates that both the asymmetry parameter ε and the isotropic component of the Knight shift increase with the increase of atomic weight of the Y element.     

Nuclear resonance measurements of CePd2Ga3

CePd₂Ga₃, a Kondo lattice exhibiting ferromagnetic order below T _C = 6.3 K, has been studied using Ga NMR technique. Measurements of the magnetic susceptibility on an oriented sample proved the strong anisotropy of this quantity, whose major component is in the basal plane. From the analysis of NMR spectra of differently oriented samples, the quadrupole parameters and the temperature-dependent anisotropic Knight-shift have been determined. While the anisotropy of the susceptibility can sufficiently account for the axial anisotropy of the ⁷¹Ga Knight shift, the in-plane anisotropy of the shift points towards dipolar effects enhanced by hybridization of the Ce-4f and Ga-s electrons.     

Magnetic properties of CuRh alloys

By means of rapid quenching techniques single phased samples of Cu_xRh_1?x(0?x?1) were obtained. For these alloys the Knight shift of ⁶³Cu and ¹⁰³Rh has been determined employing pulsed NMR at low temperatures, furthermore the magnetic susceptibility was measured for temperatures between 4.2 and 300 K. While the Knight shift of ¹⁰³Rh is dominated by s-electron contributions in spite of a high density of d-states at the Fermi level, for the susceptibility, however, the d-electron contributions prevail. In addition the susceptibility shows a pronounced maximum at about 10 at.% Cu. Using the extrapolated Knight shift of copper (x→0) we estimate a net copper hyperfine field of — 15 T in close agreement with the corresponding values for CuPd and CuPt.     

NMR studies of magnetic properties in Heusler-type Mn 3 Si

In order to microscopically investigate the magnetic properties of both paramagnetic and antiferromagnetic phases in Mn₃Si (T _N?=?23 K), the ⁵⁵Mn NMR has been carried out at temperatures between 2.2 K and 300 K. The temperature dependences of the spectrum, Knight shift (or resonance frequency shift) and spin-lattice relaxation time T ₁ of ⁵⁵Mn NMR have been measured. In the paramagnetic phase, only one resonance spectrum can be obtained. The observed spectrum is identified to be a signal corresponding to the Mn(II) site. In the antiferromagnetic phase, two different spectra corresponding to the Mn(I) and Mn(II) sites are found at the resonance frequencies of 145 and 6 MHz, respectively, by the zero field NMR at 4.2 K. From these results, the internal magnetic fields on the ⁵⁵Mn(I) and ⁵⁵Mn(II) nuclei are found to be 13.6 and 0.6 T, respectively. According to the NMR results, the helical structure in incommensurate Mn spin states is better explained compared with the transverse sinusoidal structure.     

Studies of impure cadmium oxide semiconductors using NMR,EPR and conductivity measurements

Cadmium oxide semiconductors were prepared by heating CdO which also contained hydroxide and carbonate species formed on storage. Reaction of the impurities on heating, and high temperature annealing, produced an unusually wide range of electrical conductivities, EPR spectra and NMR spectra. Changes in EPR spectra were correlated with the ¹¹³Cd shift, which was shown to be proportional to the square root of the relaxation rate, and also proportional to the line width. This allowed the Knight shift contribution to the resonance position to be separated from the paramagnetic shielding (due to covalency). The latter was found to be 234 ± 6 ppm relative to Cd(H₂O)²⁺₆. It could then be shown that the Korringa relationship (for degenerate electrons) was satisfied, with T₁TK² = 3.9 ± 0.2 × 10⁻⁶ sK. The variations of the asymmetric line shape with Knight shift were examined in the light of various models for impurity semiconductors.     

Temperature dependence of Knight shifts for 12 B in Pt

The Knight shift of a short lived β-emitting nucleus ¹²B (I = 1, T _1/2 = 20 ms) implanted into Pt has been measured as a function of temperature (140?600 K) by means of the β-NMR method. The relation between the Knight shift and the susceptibility for Pt was deduced, which shows the similar tendency to that for the case of ¹²B in Pd.     

Nuclear magnetic resonance study of potassium dihydrophosphate

A powder sample of potassium dihydrophosphate KH₂PO₄ has been studied by the ³¹P NMR method in a wide temperature range covering the ferroelectric phase transition. Changes in the position and shape of the resonance line at the transition to the ferroelectric phase have been revealed. The parameters of the chemical shift tensor of ³¹P (isotropic shift, anisotropy, and asymmetry) in the ferroelectric phase have been calculated from the experimental data. A sharp increase in the anisotropy of the tensor at the phase transition has been demonstrated. Dielectric measurements have also been carried out to verify the transition temperature.     

Muon Knight shift in palladium

The Knight shift at positive muons implanted in pure palladium has been measured as a function of temperature from 19.8 to 883 K. The Knight shift variation is strictly proportional to the Pd magnetic susceptibility with ΔK^μ/Δ_x=-(0.43±0.02) mole/emu=-(2.39±0.11)kG/μ_B. A temperature independent term K^μ(x=0)=+45±10 ppm is found. The results are discussed in terms of the electronic structure of H in Pd.     

27Al pulsed nuclear magnetic resonance study of CeAl2

The magnetic properties and the electronic structures of a rare-earth aluminum intermetallic compound CeAl₂ are investigated by magnetic susceptibility measurements and ²⁷Al pulsed nuclear magnetic resonance (NMR) techniques. The magnetic susceptibility is strongly temperature-dependent, following a Curie–Weiss law down to ∼12 K, and shows an antiferromagnetic transition at 4 K. The ²⁷Al NMR spectra show a typical powder pattern for a nuclear spin I of 5/2 with the second-order nuclear quadrupole interaction at high temperature and an additional large dipolar broadening between the 4f electron spins of cerium and the ²⁷Al nuclear spins at low temperature. The ²⁷Al NMR Knight shift follows the same temperature dependence as the magnetic susceptibility, suggesting that the ²⁷Al NMR Knight shift originates from the transferred hyperfine field of the Ce 4f electron spins with the hyperfine coupling constant of A = +5.7 kOe/μ_B. The spin-lattice relaxation rate 1/T₁ is roughly proportional to temperature, as with most non-magnetic metals at high temperature, and then strongly temperature-dependent, increasing rapidly with a peak near the antiferromagnetic transition temperature and decreasing at lower temperature. The temperature dependence of the Korringa ratio K, however, suggests that the antiferromagnetic spin fluctuation signature, which is an enhancement in the Korringa ratio, is washed out owing to the geometrical cancellation of Ce 4f fluctuations at the Al sites.     

NMR properties of hcp Ru metal — first detection of the99Ru and101Ru NMR in a paramagnetic solid

Results of nuclear magnetic resonance (NMR) measurements on hexagonal close-packed Rumetal are presented. The field spectra of both isotopes, having a nuclear spinI of 5/2, show a shape characteristic for quadrupolar disturbed NMR. From a simulation of these spectra, the electric field gradientV _zz has been determined to be (37±0.5)×10^–13 esu/cm³ in agreement with recent band structure calculations. The Knight shift tensor elements deduced from the spectra areK _x =K _y =0.46±0.02% andK _z =0.56±0.02%. These rather high and positive shifts are completely in line with that of the neighboring elements in the periodic system and have primarily to be ascribed to the Van Vleck contribution. This part of the Knight shift is also responsible for the rather strong anisotropy, that has been found.