23Na nuclear magnetic resonance investigation of the lattice distortion in α-NaxV2O5

The full temperature dependence of the electric field gradient tensor at the Na sites has been determined by nuclear magnetic resonance (NMR) in the temperature range 8–330 K in α-Na_{x 2}O₅ (x = 0.996). Above the spin-Peierls transition (T _c = 34.7 K), only a single Na site is observed in agreement with the Pmmn space group proposed to describe this compound as the first example of a 1/4-filled ladder system. Below T_c, eight distinct quadrupolar²³Na sites are observed according to the distortion wave vector k_c = (1/2, 1/2, 1/4) previously reported. In addition, the opening of a spin gap is evidenced by a rapid drop of the magnetic hyperfine shift²³K at T_c. The results are discussed in the context of a charge-order-driven spin-Peierls transition.     

Li- and V-NMR study of LiVS2

⁷Li- and ⁵¹V-NMR have been measured to make clear the electronic state in a two-dimensional triangular lattice LiVS₂. Knight shift of both ⁷Li- and ⁵¹V-NMR is almost independent of temperature below the phase transition temperature T_c of about 310 K from the paramagnetic state to non-magnetic state. The ⁵¹V- spin-lattice relaxation rate 1/T₁ reveals an exponential temperature dependence below T_c, indicating a gap structure of electronic state. These results are consistent with a non-magnetic state with a trimer singlet of V³⁺ spins below T_c.     

23Na NMR study of the local order in the Na1/2Bi1/2TiO3 structure in a weak magnetic field

The orientation dependences of the second-order quadrupole shifts of the central component in the ²³Na NMR spectrum were studied in the temperature range 293–760 K. The profile of the spectral distribution is calculated using various models of the Na_1/2Bi_1/2TiO₃ structure. The calculations agree with the experimental data for the monoclinic structure of a polar cluster with two Na displacement components: a displacement along the [111] _p direction and a small displacement statistically or dynamically disordered over six equally probable [100] _p -type directions. Tetragonal-phase nuclei and monoclinic clusters with a very small displacement component along the [111] _p direction are found to coexist and have close energies over the temperature range 580–610 K. The results obtained provide new information concerning the character of the diffuse phase transition at 610 K.     

Fullerene local order in Na2CsC60 by23Na NMR

We have investigated the alkali metal fulleride Na₂CsC₆₀ by²³Na nuclear magnetic resonance (NMR), The NMR line of the tetrahedral site is split below 170 K (T and T′ lines) similarly to the A₃C₆₀ compounds with A=Rb or K. The intensity fraction of the T′ line follows the same temperature dependence as the¹³C NMR line width. We have also found that the spectrum is independent of the cooling rate. Spin-echo double resonance measurements show that T and T′ sites are mingled on a microscopic scale. We propose that the different²³Na NMR lines correspond to different fullerene orientational environments of the tetrahedral alkaline site.     

Temperature calibration for high-temperature MAS NMR to 913 K: 63Cu MAS NMR of CuBr and CuI, and 23Na MAS NMR of NaNbO3

The solid-state phase transitions of CuBr, CuI and NaNbO₃ can be readily observed using ⁶³Cu and ²³Na high-temperature magic-angle spinning nuclear magnetic resonance spectroscopy. Temperature has large, linear effects on the peak maximum of ⁶³Cu in each solid phase of CuBr and CuI, and there is large jump in shift across each phase transition. The ²³Na MAS NMR peak intensities and the line widths in NaNbO₃ also clearly show its high-temperature transition to the cubic phase. These data can be used to calibrate high-temperature MAS NMR probes up to 913 K, which is two hundred degrees higher than the commonly-used temperature calibration based on the chemical shift of ²⁰⁷Pb in Pb(NO₃)₂.     

Study on ethyl groups with two different orientations in [N(C2H5)4]2CuBr4

The crystal structure and phase transition temperature of [N(C₂H₅)₄]₂CuBr₄ are studied using X-ray diffraction and differential scanning calorimetry (DSC); measurements revealed a tetragonal structure and the two phase transition temperatures T_C of 204 K and 255.5 K. The structural geometry near T_C is discussed in terms of the chemical shifts for ¹H magic angle spinning (MAS) nuclear magnetic resonance (NMR) and ¹³C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups are distinguishable by the ¹³C NMR spectrum. The molecular motions are discussed in terms of the spin–lattice relaxation times T_1ρ in the rotating frame for ¹H MAS NMR and ¹³C CP/MAS NMR. The T_1ρ results reveal that the ethyl groups undergo tumbling motion, and furthermore that the ethyl groups are highly mobile.     

Polarization properties of Li2−x Na x Ge4O9 (0.2 ≤ x ≤ 0.3) crystals

The polarization switching in sinusoidal fields and the pyroelectric properties of Li_2?x Na _x Ge₄O₉ (0.2 ≤ x ≤ 0.3) crystals are measured in the temperature range T _c ?T ≤ 40 K. The behavior of the P?E hysteresis loops with variations in temperature is investigated for crystals with phase transition temperatures T _c < 300 K and T _c > 300 K. It is shown that, for crystals with phase transition temperatures T _c < 300 K, the temperature dependence of the hysteresis loop exhibits a behavior typical of crystals with second-order phase transitions. The crystals with phase transition temperatures T _c > 300 K are characterized by double hysteresis loops in the temperature range T _c ?T ₁ ≈ 30 K. The correlation between the polarization properties and possible structural transformations of the Li_2?x Na _x Ge₄O₉ crystals due to the change in the concentration ratio of Na and Li ions is discussed.     

H NMR study of the phase transitions of trissarcosine calcium chloride single crystals at low temperature

The ¹H NMR line-width and spin-lattice relaxation time T₁ of TSCC single crystals were studied. Variations in the temperature dependence of the spin-lattice relaxation time were observed near 65 and 130 K, indicating drastic alterations of the spin dynamics at the phase transition temperatures. The changes in the temperature dependence of T₁ near 65 and 130 K correspond to phase transitions of the crystal. The anomalous decrease in T₁ around 130 K is due to the critical slowing down of the soft mode. The abrupt change in relaxation time at 65 K is associated with a structural phase transition. The proton spin-lattice relaxation time of this crystal also has a minimum value in the vicinity of 185 K, which is governed by the reorientation of the CH₃ groups of the sarcosine molecules. From this result, we conclude that the two phase transitions at 65 and 130 K can be discerned from abrupt variations in the ¹H NMR relaxation behavior, and that ¹H nuclei play important roles in the phase transitions of the TSCC single crystal.     

Electron spin resonance and magnetic susceptibility suggest superconductivity in Na doped WO3samples

In WO₃ doped with Na (WO₃:Na) an Electron Spin Resonance (ESR) signal with unresolved fine and/or hyperfine structure is detected and used as a probe for the state of the carriers. Using the saturation method we determined the spin-lattice relaxation rate 1/ T ₁ of these paramagnetic centers. Upon cooling below 100 K, 1/ T ₁ decreases markedly, as known to occur in NMR when a gap opens in the superconducting state. At low temperatures, 1/ T ₁ quantitatively follows BCS behavior with a gap K or 2 . The magnetic susceptibility exhibits a strong difference between magnetic-field cooled and zero-field cooled regimes below which also supports a so far unknown superconducting phase resulting from Na doping. Received 14 April 1999 and Received in final form 6 September 1999     

Complex magnetic differentiation of cobalts in Na x CoO2 with 22 K Néel temperature

Single crystals of sodium cobaltates Na _x CoO₂ with x ≈ 0.8 were grown by the floating zone technique. Using electrochemical Na de-intercalation method we reduced the sodium content in the as-grown crystals down to pure phase with 22 K Néel temperature and x ≈ 0.77. The ⁵⁹Co NMR study in the paramagnetic state of the T _N = 22 K phase permitted us to evidence that at least 6 Co sites are differentiated. They could be separated by their magnetic behavior into three types: a single site with cobalt close to non-magnetic Co³⁺, two sites with the most magnetic cobalts in the system, and the remaining three sites displaying an intermediate behavior. This unusual magnetic differentiation calls for more detailed NMR experiments on our well characterized samples.     

Sb Magnetic Resonance as a Local Probe for the Gap Formation in the Correlated Semimetal FeSb2

We report on a comparative study of the narrow-band semimetals FeSb₂ and its structural homologue RuSb₂ by means of ^121,123Sb nuclear quadrupole (NQR) and nuclear magnetic resonance (NMR) spectroscopy. From NQR for both compounds two temperature regimes could be identified by use of ¹²³(1/T ₁) measurements. Above 40 K a conventional activated behavior (with Δ/k _B ? 400 K for FeSb₂) dominates in ¹²³(1/T ₁), whereas below 40 K in both systems an unconventional ¹²³(1/T ₁) behavior with a smooth maximum at around 10 K is observed. To analyze this behavior, we propose the presence of T-dependent in-gap states forming a narrow energy level of localized spins with S = ½ near the bottom of the conduction band. These states might have originated from an inherent Sb-deficiency in both compounds. This model enables us to fit the ¹²³(1/T ₁) data in the entire investigated temperature range (2–200 K) for FeSb₂. Ab initio band structure calculations reveal more than a factor of two larger Δ value for RuSb₂ as compared with FeSb₂. This results in dissimilar behavior of ¹²³(1/T ₁) in FeSb₂ and RuSb₂ above 40 K evidencing the inefficiency of thermal activation of electrons over the large energy gap at T ≤ 300 K in RuSb₂ and dominating of quadrupole relaxation channel in RuSb₂ in this temperature range caused by phonon relaxation involving two-phonon (Raman) scattering. In addition, extra wide range field-sweep NMR measurements are performed at various temperatures on FeSb₂ and RuSb₂. The complex broad spectra could be modeled and from the shift of the ¹²¹Sb central transition the 3d component of the shift K _3d (T) could be extracted.     

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.     

The Na-TiS2 system: A critical discussion of the phase boundaries,structural and NMR studies

We present new evaluations of phase boundaries in the Na_xTiS₂ system from electrochemical intercalation and from X-ray and NMR measurements in samples intercalated using the liquid ammonia technique. After a critical discussion of the influence of the method of intercalation on the phase limits we present an extensive NMR study of the system. ²³Na quadrupolar coupling determinations support the fact that the low concentration (x < 0.25) phase II is a stage 2 phase. ²³Na Knight shift results show that the transition from the Ib trigonal prismatic phase to the Ia trigonal antiprismatic phase with increasing Na concentration takes place with a change in the electronic band structure. The stability of this phase is discussed in terms of the balance between elastic and electronic energies.     

SDW in the 2D Compound CuFeTe2

In a previous work (ICAME'97) we presented the Mössbauer results for a non-stoichiometric sample of the quasi-two-dimensional (2D) dichalcogenide CuFeTe₂, where a Spin Density Wave (SDW) ground state with T _SDW=256±15 K was proposed. Here we report the study of the magnetic and electric properties determined by magnetic susceptibility, Mössbauer spectroscopy and resistance measurements, of an almost stoichiometric sample prepared by the vertical Bridgman growth technique. The SDW behavior is supported by the results obtained by the following different techniques: Magnetic susceptibility: A magnetic transition is observed at T _SDW=308 K with a Pauli paramagnetic behavior above this temperature. Mössbauer effect: The shape of the spectra and the thermal evolution of the hyperfine field are characteristic of the SDW's in quasi-2D systems. Electrical resistance: There is a metal–semiconductor transition along the layers as the temperature decreases indicating the opening of a gap at the Fermi level.     

Hyperfine magnetic interactions of 57Fe nuclei in NaFeAs arsenide

The results of the Mössbauer effect studies of layered NaFeAs arsenide in a wide temperature range are presented. The measurements at T > T _N demonstrate that the main part (～90%) of iron atoms are in the low-spin state Fe²⁺. The other atoms can be attributed to the impurity NaFe₂As₂ phase or to the extended defects in NaFeAs. The structural phase transition (at T _S ≈ 55 K) does not produce any effect on hyperfine parameters (δ, Δ) of iron atoms. At T < T _N, the spectra exhibit the existence of a certain distribution of the hyperfine magnetic field (H _Fe) at ⁵⁷Fe nuclei, indicating the inhomogeneity of the magnetic environment around iron cations. The analysis of the temperature behavior of the distribution function p(H _Fe) allows us to determine the temperature of the magnetic phase transition (T _N = 46 ± 2 K). It has been found that the magnetic ordering in the iron sublattice has a two-dimensional type. The analysis of the H _Fe(T) dependence in the framework of the Bean-Rodbell model reveals a first-order magnetic phase transition accompanied by a drastic change in the electron contributions to the main component (V _ZZ ) and the asymmetry parameter (η) of the tensor describing the electric field gradient at ⁵⁷Fe nuclei.     

Magnetic and structural anomalies of Na<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C<Subscript>60</Subscript> (n = 2, 3)

Sodium fullerides Na _n C60 (n = 2, 3) have been synthesized by a liquid phase reaction and investigated with X-ray diffraction (XRD), nuclear magnetic resonance (NMR), electron paramagnetic resonance, and differential thermal analysis. XRD data indicate that the crystal structure of Na₂C₆₀ at 300 K is face centered cubic (FCC). A phase transition from primitive cubic to FCC crystal structure has been observed in this work in Na₂C₆₀ fulleride at 290 K. The transition is accompanied by the step-like change of paramagnetic susceptibility. The crystal structure of Na₃C₆₀ is more complicated than, and different from, what has been reported in the literature. A nearly seven-fold increase of paramagnetic susceptibility with increasing temperature has been observed in the Na₃C₆₀ fulleride at 240–260 K. In the same temperature range, a new line at about 255 ppm appears in the ²³Na NMR spectrum, indicating a significant increase of electron density near the Na nucleus. The observed effect can be explained by a metal-insulator transition caused by a structural transition.     

Electron spin-lattice relaxation in noncommon metals YBa2Cu3Ox and Rb1C60

Using an original modulation technique, the electron spin-lattice relaxation have been investigated in two noncommon metals: YBa₂Cu₃O_x, high-T_c material doped with 1% Gd, and Rb₁C₆₀, linear polymer phase fulleride. In the first case, the Korringa-like temperature dependence of the Gd³⁺ longitudinal relaxation time T₁, is found forx = 6.59 in a wide temperature range 4.2 <T < 200 K, both above and below T_c = 56 K. Atx = 6.95 (T_c = 90 K), the T₁ behavior within 50 <T < 200 K is evidently affected by spin gap opening with the gap value of about 240 K. At 200 K, an unexpected acceleration of the relaxation rate takes place, suggesting some change in the relaxation mechanism. The data are discussed in terms of the Barnes-Plefke theory with allowance made for microscopic separation of the normal and superconducting phases. In Rb₁C₆₀, the evolution of the ESR line and relaxation rates have been studied accurately in the range of the metal-insulator transition (below 50 K). Interpretation is suggested which takes into account breaking down the relaxation bottleneck due to opening of the energy gap near the Fermi surface. The gap value of about 100 cm^?1 is estimated from the analysis of relaxation rates, lineshape and spin susceptibilities.     

Domain configuration and dynamic processes in orthorhombic NaCN studied by 23Na NMR satellite lines and relaxation times

The orientational dependences of the ²³Na NMR spectra which were measured in a NaCN single crystal below T_c1 are related to the EFG tensor at the Na sites in different domains. The results are consistent with the assumption that 12 different domains may arise in the orthorhombic phase. Below T_c1 also the temperature dependences of the spin relaxation times T₁ and T_1ρ of the ²³Na nucleus were measured and related to dynamic processes. Particularly the activation energy and the frequency of the flip motions of the CN^--dipoles are determined.     

Nuclear magnetic resonance studies of CePd2In and LaPd2In at low temperatures

We report on In nuclear magnetic resonance (NMR) and nuclear quadrupolar resonance (NQR) measurements on the new heavy-electron compound CePdZIn over a wide temperature range, from 45 mK up to 30 K. CePd₂In undergoes an antiferromagnetic (AF) phase transition at T _N = 1.23 K involving small localised Ce moments of 0.11 μ_B. In zero field, the spin-lattice relaxation rate T ₁ ^?1 (T) shows remarkable changes in its temperature dependence. Above 3 K, T ₁ ^?1 is constant and 850 sec^?1. Between T _N and 2T _N, (T ₁ T)^?1 = 330 (Ksec)^?1, but rapidly decreases below T _N. A Korringatype relaxation, characteristic for simple metals at low temperatures, with (T ₂ T)^?1 = 17(Ksec)¹ is resumed below 0.6 K. This value is an order of magnitude larger than (T ₁ T)^?1 for LaPd₂In and therefore is associated with low-energy excitations of the itinerant charge carriers with 4f symmetry. The T ₁ ^?1 data at various non-zero magnetic fields fall on a single curve when plotted as a function of (T/H) if H exceeds 3.5 T. Thus the AF ordering, the 4f moment fluctuations and the Kondo screening are drastically suppressed by the application of fields H of the order of 3.5 T.     

High-Temperature Phase Transition in N(CH3)4CdCl3 Studied Using Static NMR and MAS NMR

To clarify the nature of microscopic structural changes of N(CH₃)₄CdCl₃ at high temperatures, the nuclear magnetic resonance (NMR) spectra of the protons and carbons in N(CH₃)₄CdCl₃ were measured. NMR studies of the ¹H and ¹³C spin–lattice relaxation time, T _1ρ, in the rotating frame were also performed. No changes in the T _1ρ of ¹H and ¹³C associated with the N(CH₃)₄ groups were observed at the high-temperature transition from phase I to phase I′. However, the ¹⁴N NMR spectra reflected changes in the structural geometry during the transition to phase I′, indicating that this transition is driven by N(CH₃)₄.