Nuclear Spin-lattice Relaxation Rate Research Articles

Anion and Cation Dynamics in Mixed-Anion Hydroborate Na3(BH4)(B12H12): 1H, 11B, and 23Na NMR Studies

Sodium borohydride-closo-hydroborate Na3(BH4)(B12H12) exhibits high room-temperature ionic conductivity and high electrochemical stability. To study the dynamical properties of this mixed-anion compound at the microscopic level, we have measured the 1H, 11B, and 23Na nuclear magnetic resonance spectra and nuclear spin-lattice relaxation rates over the temperature range of 8–573 K. Our 1H and 11B spin-lattice relaxation measurements have revealed two types of reorientational jump motion. The faster motional process attributed to reorientations of the [BH4]− anions is characterized by an activation energy of 159 meV, and the corresponding reorientational jump rate reaches ~108 s−1 near 130 K. The slower process ascribed to reorientations of the larger [B12H12]− anions is characterized by an activation energy of 319 meV, and the corresponding reorientational jump rate reaches ~108 s−1 near 240 K. The results of the 23Na nuclear magnetic resonance measurements are consistent with the fast long-range diffusion of Na+ ions in Na3(BH4)(B12H12). The diffusive jump rate of Na+ is found to reach ~104 s−1 at 300 K and ~8 × 108 s−1 at 530 K. A comparison of these jump rates with the ionic conductivity data suggests the importance of correlations between diffusing ions.

Narrowly avoided spin-nematic phase in BaCdVO(PO4)2: NMR evidence

We present a P31 NMR investigation of BaCdVO(PO4)2 focusing on the nearly saturated regime between μ0Hc1=4.05T and μ0Hc2=6.5T, which used to be considered a promising candidate for a spin-nematic phase. NMR spectra establish the absence of any dipolar order there, whereas the weak field dependence of the magnetization above Hc1 is accounted for by Dzyaloshinskii-Moriya interaction terms. The low-energy spin dynamics (fluctuations), measured by the nuclear spin-lattice relaxation rate T1−1, confirms the continuity of this phase and the absence of any low-temperature phase transition. Unexpectedly, the spin dynamics above Hc1 is largely dominated by two-magnon processes, which is expected the saturation field of a spin-nematic phase, but not inside. This shows that BaCdVO(PO4)2 is indeed close to a spin-nematic instability; however, this phase is stabilized. We thus confirm recent theoretical predictions that the spin-nematic phase can be stabilized, at most, in an extremely narrow field range close to saturation or is rather narrowly avoided [Jiang , ]. Published by the American Physical Society 2024

Nuclear spin-lattice relaxation rate in disordered paramagnetic diluted magnetic semiconductors

Nuclear spin-lattice relaxation rate in disordered paramagnetic diluted magnetic semiconductors

Anion and cation dynamics in a carbon-substituted cesium closo-hydroborate CsCB11H12: 1H and 133Cs NMR studies

Cesium monocarba-hydroborate CsCB11H12 belongs to the family of alkali-metal closo- hydroborate salts which are considered as promising solid electrolytes for battery applications. To study the dynamical properties of this compound at the microscopic level, we have measured the 1H and 133Cs nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates over the temperature range of 80–434 K. Our measurements have revealed a coexistence of two types of reorientational jump processes of the complex [CB11H12]− anions. For the faster of these processes characterized by the average activation energy of 310 meV, the anion reorientations are not “frozen” at the NMR frequency scale down to 120 K. The behavior of the 133Cs NMR line width in CsCB11H12 is consistent with the onset of long-range diffusive motion of Cs+ ions at the frequency scale of ∼104 s−1 above 340 K, and the distinct effects of the diffusive Cs+ jumps on both the 1H and 133Cs spin-lattice relaxation rates become observable above 380 K.

Gapless fermionic excitation in the antiferromagnetic state of ytterbium zigzag chain

The emergence of charge-neutral fermionic excitations in magnetic systems is one of the unresolved issues in recent condensed matter physics. This type of excitations has been observed in various systems, such as low-dimensional quantum spin liquids, Kondo insulators, and antiferromagnetic insulators. Here, we report the presence of a pronounced gapless spin excitation in the low-temperature antiferromagnetic state of YbCuS2 semiconductor, where trivalent ytterbium atoms form a zigzag chain structure. We confirm the presence of this gapless excitations by a combination of experimental probes, namely 63/65Cu-nuclear magnetic resonance and nuclear quadrupole resonance, as well as specific heat measurements, revealing a linear low-temperature behavior of both the nuclear spin-lattice relaxation rate 1/T1 and the specific heat. This system provides a platform to investigate the origin of gapless excitations in spin chains and the relationship between emergent fermionic excitations and frustration.

Magnetic resonance study of novel detonation nanodiamonds originated from non-conventional explosives

Detonation nanodiamonds (DND) are conventionally synthesized from a mixture of trinitrotoluene (TNT) and hexogen (RDX) explosives. It is generally believed that the internal structure of DNDs, which consists of a diamond core covered with a partially disordered shell, is very similar in all DNDs. Variations of the properties of DNDs are usually associated with the surface functionalization of the hydrogen-terminated surface with various chemicals to obtain a family of different nanodiamonds. In this paper, we report on the synthesis, electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) study of novel DNDs synthesized from a few non-conventional explosives, which have not previously been used for this purpose. We show that DNDs synthesized from different explosive precursors display different ratios of carbon atoms in the core and shell. The variation of this ratio correlates well with variations in the content of paramagnetic defects and 13C nuclear spin-lattice relaxation rates. The presented data advances new opportunities for controllable synthesis of DNDs with engineered properties.

Nuclear spin relaxation in aqueous paramagnetic ion solutions.

A Brownian shell model describing the random rotational motion of a spherical shell of uniform particle density is presented and validated by molecular dynamics simulations. The model is applied to proton spin rotation in aqueous paramagnetic ion complexes to yield an expression for the Larmor-frequency-dependent nuclear magnetic resonance spin-lattice relaxation rate T_{1}^{-1}(ω) describing the dipolar coupling of the nuclear spin of the proton with the electronic spin of the ion. The Brownian shell model provides a significant enhancement to existing particle-particle dipolar models without added complexity, allowing fits to experimental T_{1}^{-1}(ω) dispersion curves without arbitrary scaling parameters. The model is successfully applied to measurements of T_{1}^{-1}(ω) from aqueous manganese(II), iron(III), and copper(II) systems where the scalar coupling contribution is known to be small. Appropriate combinations of Brownian shell and translational diffusion models, representing the inner and outer sphere relaxation contributions, respectively, are shown to provide excellent fits. Quantitative fits are obtained to the full dispersion curve of each aquoion with just five fit parameters, with the distance and time parameters each taking a physically justifiable numerical value.

Calorimetric measurement of nuclear spin-lattice relaxation rate in metals

The quasiparticle density of states in correlated and quantum-critical metals directly probes the effect of electronic correlations on the Fermi surface. Measurements of the nuclear spin-lattice relaxation rate provide one such experimental probe of quasiparticle mass through the electronic density of states. By far the most common way of accessing the spin-lattice relaxation rate is via nuclear magnetic resonance and nuclear quadrupole resonance experiments, which require resonant excitation of nuclear spin transitions. Here we report non-resonant access to spin-lattice relaxation dynamics in AC-calorimetric measurements. The nuclear spin-lattice relaxation rate is inferred in our measurements from its effect on the frequency dispersion of the thermal response of the calorimeter-sample assembly. We use fast, lithographically-defined nanocalorimeters to access the nuclear spin-lattice relaxation times in metallic indium from 0.3~K to 7~K and in magnetic fields up to 35~T.

Low-Temperature Magnetic Fluctuations Investigated by 125Te-NMR on the Uranium-Based Superconductor UTe2

To investigate the static and dynamic magnetic properties on the uranium-based superconductor UTe2, we measured the NMR Knight shift K and the nuclear spin–lattice relaxation rate 1/T1 in H || a by 125Te-NMR on a 125Te-enriched single-crystal sample. 1/T1T in H || a is much smaller than 1/T1T in H || b and c, and magnetic fluctuations along each axis are derived from the 1/T1T measured in H parallel to all three crystalline axes. The magnetic fluctuations are almost identical at two Te sites and isotropic at high temperatures, but become anisotropic below 40 K, where heavy-fermion state is formed. The character of magnetic fluctuations in UTe2 is discussed with the comparison to its static susceptibility and the results on other U-based superconductors. It is considered that the magnetic fluctuations probed with the NMR measurements are determined by the magnetic properties inside the two-leg ladder formed by U atoms, which are dominated by the qa = 0 ferromagnetic fluctuations.

Dynamical properties of the magnesium borohydride – ethylenediamine compound Mg(en)1.2(BH4)2: A nuclear magnetic resonance study

The magnesium borohydride – ethylenediamine (en) compound Mg(en)1.2(BH4)2 exhibits high Mg-ion conductivity above room temperature. To study the dynamical properties of this compound and its partially deuterium-substituted counterpart, we have measured the 1H, 2D, and 11B nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates over a wide temperature range (6–324 K). Our measurements have revealed a coexistence of four types of BH4 reorientational jump processes with different activation energies. For the fastest of these processes characterized by the activation energy of 47(3) meV, the unusually high reorientational mobility is retained down to low temperatures, so that the corresponding H jump rate is of the order of 108 s−1 near 70 K. The presence of fast reorientational motion of [BH4]− anions in Mg(en)1.2(BH4)2 supports the idea that anion reorientations may facilitate the cation diffusion. In the studied temperature range, we have not found any distinct signs of localized motion of the ethylenediamine molecules or their fragments at the NMR frequency scale.

Observation of multigap and coherence peak in the noncentrosymmetric superconductor CaPtAs: As75 nuclear quadrupole resonance measurements

We present synthesis and $^{75}$As-nuclear quadrupole resonance (NQR) measurements for the noncentrosymmetric superconductor CaPtAs with a superconducting transition temperature $T_c$ of $\sim 1.5$ K. We discovered two different forms of CaPtAs during synthesis; one is a high-temperature tetragonal form that was previously reported, and the other is a low-temperature form consistent with the orthorhombic structure of CaPtP. According to the $^{75}$As-NQR measurement for superconducting tetragonal CaPtAs, the nuclear spin-lattice relaxation rate $1/T_1$ has an obvious coherence peak below $T_c$ and does not follow a simple exponential variation at low temperatures. These findings indicate that CaPtAs is a multigap superconductor and a large $s$-wave component.

Giant Density of States Enhancement Driven by a Zero-Mode Landau Level in Semimetallic Black Phosphorus under Pressure.

Dirac fermion systems form a unique Landau level at the Fermi level-the so-called zero mode-whose observation itself will provide strong evidence of the presence of Dirac dispersions. Here, we report the study of semimetallic black phosphorus under pressure by ^{31}P-nuclear magnetic resonance measurements in a wide range of magnetic field up to 24.0T. We have found a field-induced giant enhancement of 1/T_{1}T, where 1/T_{1} is the nuclear spin lattice relaxation rate: 1/T_{1}T at 24.0T reaches more than 20 times larger than that at 2.0T. The increase in 1/T_{1}T above 6.5T is approximately proportional to the squared field, implying a linear relationship between the density of states and the field. We also found that, while 1/T_{1}T at a constant field is independent of temperature in the low-temperature region, it steeply increases with temperature above 100K. All these phenomena are well explained by considering the effect of Landau quantization on three-dimensional Dirac fermions. The present study demonstrates that 1/T_{1} is an excellent quantity to probe the zero-mode Landau level and to identify the dimensionality of the Dirac fermion system.

Field evolution of magnetic phases and spin dynamics in the honeycomb lattice magnet Na2Co2TeO6 : Na23 NMR study

We report on the results of 23Na NMR in the honeycomb lattice magnet Na2Co2TeO6 which has been nominated as a Kitaev material. Measurements of magnetic shift and width of the NMR line as functions of temperature and magnetic field show that a spin-disordered phase does not appear up to a field of 9 T. In the antiferromagnetic phase just below the Neel temperature TN, we find a temperature region extending down to ~TN/2 where the nuclear spin-lattice relaxation rate 1/T1 remains enhanced and is further increased by a magnetic field. This region crosses over to a low temperature region characterized by the rapidly decreasing 1/T1 which is less field-sensitive. These observations suggest incoherent spin excitations with a large spectral weight at low energies in the intermediate temperature region transforming to more conventional spin-wave excitations at low temperatures. The drastic change of the low-energy spin dynamics is likely caused by strong damping of spin waves activated only in the intermediate temperature region, which may be realized for triple-q magnetic order possessing partially-disordered moments as scattering centers of spin waves. In the paramagnetic phase near TN, dramatic field suppression of 1/T1 is observed. From analysis of the temperature dependence of 1/T1 based on the renormalized-classical description of a two-dimensional quantum antiferromagnet, we find the field-dependent spin stiffness constant that scales with TN as a function of magnetic field. This implies field suppression of the energy scale characterizing both two-dimensional spin correlations and three-dimensional long-range order, which may be associated with an increasing effect of frustration in magnetic fields.

Triangular Magnet Emergent from Noncentrosymmetric Sr0.94Mn0.86Te1.14O6 Single Crystals.

We report the successful growth of high-quality single crystals of Sr0.94Mn0.86Te1.14O6 (SMTO) using a self-flux method. The structural, electronic, and magnetic properties of SMTO are investigated by neutron powder diffraction (NPD), single-crystal X-ray diffraction (SCXRD), thermodynamic, and nuclear magnetic resonance techniques in conjunction with density functional theory calculations. NPD unambiguously determined octahedral (trigonal antiprismatic) coordination for all cations with the chiral space group P312 (no. 149), which is further confirmed by SCXRD data. The Mn and Te elements occupy distinct Wyckoff sites, and minor anti-site defects were observed in both sites. X-ray photoelectron spectroscopy reveals the existence of mixed valence states of Mn in SMTO. The magnetic susceptibility and specific heat data evidence a weak antiferromagnetic order at TN = 6.6 K. The estimated Curie-Weiss temperature θCW = -21 K indicates antiferromagnetic interaction between Mn ions. Furthermore, both the magnetic entropy and the 125Te nuclear spin-lattice relaxation rate showcase that short-range spin correlations persist well above the Néel temperature. Our work demonstrates that Sr0.94(2)Mn0.86(3)Te1.14(3)O6 single crystals realize a noncentrosymmetric triangular antiferromagnet.

Static and dynamic magnetic properties of the spin- triangle lattice antiferromagnet Na3Fe(PO4)2 studied by 31P NMR

31P nuclear magnetic resonance (NMR) measurements have been carried out to investigate the magnetic properties and spin dynamics of Fe3+ (S = 5/2) spins in the two-dimensional triangular lattice (TL) compound Na3Fe(PO4)2. The temperature (T) dependence of nuclear spin-lattice relaxation rates () shows a clear peak around Néel temperature, K, corresponding to an antiferromagnetic (AFM) transition. From the temperature dependence of NMR shift (K) above , an exchange coupling between Fe3+ spins was estimated to be K using the spin-5/2 Heisenberg isotropic-TL model. The temperature dependence of divided by the magnetic susceptibility (χ), , above proves the AFM nature of spin fluctuations below in the paramagnetic state. In the magnetically ordered state below , the characteristic rectangular shape of the NMR spectra is observed, indicative of a commensurate AFM state in its ground state. The strong temperature dependence of 1/T 1 in the AFM state is well explained by the two-magnon (Raman) process of the spin waves in a 3D antiferromagnet with a spin-anisotropy energy gap of 5.7 K. The temperature dependence of sublattice magnetization is also well reproduced by the spin waves. Those results indicate that the magnetically ordered state of Na3Fe(PO4)2 is a conventional 3D AFM state, and no obvious spin frustration effects were detected in its ground state.

Al27 NMR insight into the phase transition in BaFe2Al9

We have applied $^{27}\mathrm{Al}$ nuclear magnetic resonance (NMR) spectroscopy to investigate the iron-based aluminide of $\mathrm{Ba}{\mathrm{Fe}}_{2}{\mathrm{Al}}_{9}$. This material has been a subject of current interest due to indications of charge density wave behavior below the transition temperature ${T}_{C}\ensuremath{\simeq}100$ K. Two sets of the $^{27}\mathrm{Al}$ NMR resonance lines that are associated with two nonequivalent crystallographic aluminum sites have been well resolved. We have discussed the obtained electric field gradient and anisotropic Knight shift for each individual aluminum site, revealing the strong $ab$ plane bonding configuration for the structural properties of $\mathrm{Ba}{\mathrm{Fe}}_{2}{\mathrm{Al}}_{9}$. Pronounced features in the isotropic Knight shift and nuclear spin-lattice relaxation rate have been observed in the vicinity of ${T}_{C}$. Furthermore, the detailed $^{27}\mathrm{Al}$ NMR analyses have provided evidence for the decrease of the electronic density of states upon lowering temperature below ${T}_{C}$.

Enhancement of charge-neutral fermionic excitations near the spin-flop transition in the magnetic Kondo material YbIr3Si7

The new Kondo material YbIr$_3$Si$_7$, similar to other Kondo insulators, has been reported to exhibit charge-neutral fermionic excitations through measurements of specific heat and thermal conductivity at low temperatures. We performed $^{29}$Si-NMR on YbIr$_3$Si$_7$ to investigate the magnetic response of charge-neutral fermions from a microscopic perspective. In low magnetic fields parallel to the $c$ axis, a single NMR peak in the paramagnetic state splits into three peaks below $T_{\rm N}$. In contrast, only a slight shift of the single NMR peak was observed in high magnetic fields. This spectral change as a function of the $c$-axis magnetic field is interpreted as spin-flop transition, at which the magnetic moments oriented along the $c$ axis (AF-I phase) are rotated to the $ab$ plane with ferromagnetic component along the $c$-axis (AF-II phase). In the vicinity of the spin-flop magnetic field $H_{\rm M}$, nuclear spin-lattice relaxation rate $1/T_1$ was found to be proportional to temperature at low temperatures, indicating the existence of charge-neutral fermions. Furthermore, a peak of $1/T_1$ vs. the $c$-axis magnetic field suggests that the charge-neutral fermions in YbIr$_3$Si$_7$ are closely related to its magnetic properties. Our findings shed light on the origin of charge-neutral fermions in insulators.

Microscopic properties of Mo4Ga20Sb intermetallic superconductor in normal and superconducting states as evidenced by NMR and NQR spectroscopy

A detailed study of novel intermetallic superconductor Mo4Ga20Sb (Tc = 6.6 K) by means of 69,71Ga nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) spectroscopy was performed to gain insight into the superconducting pairing mechanism and gap characteristics, as well as into the normal-state electronic properties on a microscopic scale. An unexpected step-like increase of the 69Ga1 NQR linewidth was observed at Tc with decreasing temperature, which may indicate coexistence of several superconducting phases on a microscopic scale with slightly different Tc values. Above 140 K, the NQR linewidth decreases rapidly with increasing temperature due to possible oscillatory and/or rotational modes of the gallium cluster network at the elevated temperatures. Nuclear spin lattice relaxation rate 1/T1 of 69Ga nuclei in the Ga1 position follows Korringa law characteristic for the compounds with good metallic conductivity. The calculated Korringa ratio S< 1 indicates the presence of antiferromagnetic correlations in Mo4Ga20Sb, in agreement with the magnetic susceptibility data. Below Tc, a pronounced intensive Hebel-Slichter peak was observed indicating s-wave superconductivity without point or line nodes in the k-space (full gap s-wave superconductivity). We have demonstrated that the best fit of the experimental data is achieved using two s-wave superconducting gaps of 13 K and 6 K with relative weights of 0.8 and 0.2, respectively. The obtained weighted average value of 11.6 K is consistent with the specific heat value of Δ = 12.05 K.

139La-NMR Study of Spin Dynamics Coupled with Hole Mobility in T*-type La0.86Eu0.86Sr0.28CuO4−δ

In T*-type cuprate oxides with five-oxygen coordination, the relationship between spin correlations and doped carriers has not been well understood. To clarify this relationship, and the magnetic and superconducting (SC) properties of T*-type cuprate oxides, we performed 139La-nuclear magnetic resonance (NMR) and electrical resistivity measurements on as-sintered (AS) and oxidation-annealed (OA) polycrystalline T*-type La0.86Eu0.86S0.28CuO4 (LESCO) to investigate its magnetic and SC properties. Upon cooling, the NMR spectrum of AS LESCO broadened below 3 K, where the nuclear spin–lattice relaxation rate 1/T1 with respect to the temperature exhibited a maximum, indicating the appearance of static magnetism. The temperature dependence of 1/T1 between 3 and 20 K was similar to that of resistivity, which displays semiconducting behavior. Furthermore, it was found that the energy scales of the transport gap and spin dynamics were comparable. These results suggest a close connection between the mobility of the doped carriers and low-energy spin dynamics, as reported for lightly doped T-type La2−xSrxCuO4. In the OA SC sample, we confirmed the absence of a magnetic order and the linear relation between 1/T1 and T above 10 K. These results suggest that the magnetic state coupled with holes markedly changes to the weakly correlated metallic state by oxidation annealing in the T*-type LESCO with x = 0.28.

Superconductivity and Charge Ordering in BEDT-TTF Based Organic Conductors with β″-Type Molecular Arrangement

Exotic superconductivity that appears near the charge ordering instability has attracted significant interest since the beginning of superconducting study. The discovery of possible coexistence of charge ordering and superconductivity in cuprates and kagome metals has further fascinated researchers in recent years. In this review, we focus on the BEDT-TTF-based organic superconductor with β″-type molecular packing sequence, which shows the charge ordering transition in the very vicinity of superconducting transition, and summarize the experimental results reported up to the present. At the charge ordering temperature, ultrasonic measurement detects the softening of the crystal lattice, and 13C-NMR measurement shows an increase in nuclear spin-lattice relaxation rate divided by temperature 1/T1T. These results suggest that low-energy dynamics are activated near the charge ordering transition, leading us to invoke the charge-fluctuation mediated superconducting pairing mechanism.