Spin-lattice Relaxation Rate Research Articles

Magnetic inhomogeneity in charge-ordered La1.885Sr0.115CuO4 studied by NMR

We report the inverse Laplace transform (ILT) analysis of the $^{139}$La nuclear spin-lattice relaxation rate $1/T_1$ in charge ordered La$_{1.885}$Sr$_{0.115}$CuO$_4$ ($T_{charge} \sim 80$K, $T_{c} \simeq T_{spin}^{neutron}=30$K), and shed new light on its magnetic inhomogeneity. We deduce the probability density function $P(1/T_{1})$ of the distributed $1/T_1$ (i.e. the histogram of distributed $1/T_1$) by taking the inverse Laplace transform of the experimentally observed nuclear magnetization recovery curve $M(t)$. We demonstrate that spin freezing sets in in some domains precisely below the onset of charge order at $T_{charge}$, but their volume fraction grows only gradually toward $T_{c}$. Nearly a half of the sample volume exhibits properties expected for canonical high $T_c$ cuprates without charge order even near $T_c$. Our findings explain why charge order does not suppress $T_c$ of La$_{1.885}$Sr$_{0.115}$CuO$_4$ as significantly as in La$_{1.875}$Ba$_{0.125}$CuO$_4$.

La139 NMR investigation of the interplay between lattice, charge, and spin dynamics in the charge-ordered high- Tc cuprate La1.875Ba0.125CuO4

We investigate the interplay between the lattice, charge, and spin dynamics in charge ordered high $T_c$ cuprate La$_{1.875}$Ba$_{0.125}$CuO$_{4}$ ($T_{c} =4$~K) based on the inverse Laplace transform (ILT) analysis of the $^{139}$La nuclear spin-lattice relaxation rate $1/T_1$ (dubbed ILTT$_{1}$ analysis here after). A major thrust of the ILTT$_{1}$ analysis is that one can deduce the probability density function $P(1/T_1)$ of distributed $1/T_1$. We demonstrate that $1/T_{1}^{lm}$, defined as the log-mean (i.e. the center of gravity on a logarithmic scale) of $P(1/T_1)$, can be well approximated by $1/T_{1}^{str}$ deduced from the phenomenological stretched fit, however, $P(1/T_1)$ can provide much richer insight into how the lattice, charge, and spin fluctuations and their distribution develop near and below the long range charge order at $T_{charge} \sim 54$~K. Upon entering the charge ordered state, a divergent increase of $1/T_{1}^{lm}$ toward the spin ordering at $T_{spin}^{\mu SR} \simeq 35$~K is accompanied by an asymmetric broadening of $P(1/T_1)$. Even deep inside the charge ordered state, $1/T_{1}$ at a gradually diminishing fraction of $^{139}$La sites continues to slow down as temperature is lowered, as expected for canonical superconducting CuO$_2$ planes without enhanced spin fluctuations. The fraction of such canonical $^{139}$La sites almost disappears by $\simeq 40$~K. In contrast, nearly a half of the $^{139}$La sites in La$_{1.885}$Sr$_{0.115}$CuO$_{4}$ ($T_{charge} \simeq 80$~K) still exhibits the canonical behavior without enhanced spin fluctuations even near its $T_{c} = 31$~K. These contrasting behaviors explain why superconductivity in La$_{1.875}$Ba$_{0.125}$CuO$_{4}$ is more strongly suppressed than in La$_{1.885}$Sr$_{0.115}$CuO$_{4}$ despite the lower onset temperature of the charge order.

NMR Studies of Bicontinuous Liquid Crystalline Phases of Cubic Symmetry: Interpretation of Frequency-Dependent Relaxation Rates.

Extensive deuterium NMR relaxation data are presented for two specifically deuterium labeled surfactants forming bicontinuous cubic phases with water. 2H spin-lattice (R1) and spin-spin (R2) relaxation rates were measured over an extended frequency range from 2 to 60 MHz. The data are interpreted with an existing theoretical framework for spin relaxation in bicontinuous cubic phases, which takes its starting point in the description of bicontinuous phases using periodic minimal surfaces. We show that the theory succeeds in accounting for the data and that the defining parameters of the theory, correlation times and order parameters, are in agreement with related data in other surfactant phase situations. Specifically, we obtain the surfactant self-diffusion coefficient over the minimal surface in one unit cell and show that it is in agreement with the corresponding macroscopic NMR diffusion data. By measuring two additional NMR relaxation parameters for each carbon on the surfactant hydrocarbon tail, we demonstrate how order parameter and correlation time profiles can be obtained. Finally, we analyze published molecular dynamics trajectories for a bicontinuous cubic phase. The analysis provides further support for the theoretical framework used to interpret relaxation data.

Selective observation of sublattice magnetization in the molecular π−d system λ−(BEDT−STF)2FeCl4 studied by C13 NMR

We have performed $^{13}\mathrm{C}$ NMR measurements on $\ensuremath{\lambda}\ensuremath{-}{(\mathrm{BEDT}\ensuremath{-}\mathrm{STF})}_{2}{\mathrm{FeCl}}_{4}$ to reveal the mechanism of unconventional paramagneticlike behavior observed in $\ensuremath{\lambda}$-type molecular $\ensuremath{\pi}\ensuremath{-}d$ systems. $^{13}\mathrm{C}$ NMR spectra and nuclear spin-lattice relaxation rate $1/{T}_{1}$ revealed that the $\ensuremath{\pi}$ and $3d$ electron systems undergo an antiferromagnetic transition simultaneously at 16 K with the assistance of the $\ensuremath{\pi}\ensuremath{-}d$ interaction. We found that the sublattice magnetizations of the $\ensuremath{\pi}$ and $3d$ spins show different temperature dependence below ${T}_{\mathrm{N}}$, which is derived from the magnetic coupling between the two sublattice systems with different magnetic natures. We discuss the relationship between the two different magnetization processes and the unconventional magnetic behavior in $\ensuremath{\lambda}$-type molecular $\ensuremath{\pi}\ensuremath{-}d$ system.

Pressure-induced evolution of band structure in black phosphorus studied by P31 NMR

Two-dimensional layered semiconductor black phosphorus (BP), a promising pressure induced Dirac system as predicted by band structure calculations, has been studied by $^{31}$P-nuclear magnetic resonance. Band calculations have been also carried out to estimate the density of states $D(E)$. The temperature and pressure dependences of nuclear spin lattice relaxation rate $1/T_1$ in the semiconducting phase are well reproduced using the derived $D(E)$, and the resultant pressure dependence of semiconducting gap is in good accordance with previous reports, giving a good confirmation that the band calculation on BP is fairly reliable. The present analysis of $1/T_1$ data with the complemental theoretical calculations allows us to extract essential information, such as the pressure dependences of $D(E)$ and chemical potential, as well as to decompose observed $1/T_1$ into intrinsic and extrinsic contributions. An abrupt increase in $1/T_1$ at 1.63GPa indicates that the semiconducting gap closes, resulting in an enhancement of conductivity.

Phonon-assisted proton tunneling in the hydrogen-bonded dimeric selenates of Cs3H(SeO4)2.

In phases III and IV of Cs3H(SeO4)2, the vibrational state and intrabond transfer of the proton in the dimeric selenates are systematically studied with a wide range of absorbance spectra, a spin-lattice relaxation rate of 1H-NMR (T1 -1), and DFT calculations. The OH stretching vibrations have extremely broad absorption at around 2350 (B band) and 3050 cm-1 (A band), which originate from the 0-1 and 0-2 transitions in the asymmetric double minimum potential, respectively. The anharmonic-coupling calculation makes clear that the A band couples not only to the libration but also to the OH bending band. The vibrational state (nano-second order) is observed as the response of the proton basically localized in either of the two equivalent sites. The intrabond transfer between those sites (pico-second order) yields the protonic fluctuation reflected in T1 -1. Together with the anomalous absorption [νp2 phonon, libration, tetrahedral deformation (δ440), and 610-cm-1 band], we have demonstrated that the intrabond transfer above 70 K is dominated by the thermal hopping that is collectively excited at 610 cm-1 and the phonon-assisted proton tunneling (PAPT) relevant to the tetrahedral deformation [PAPT(def)]. Below 70 K, T1 -1 is largely enhanced toward the antiferroelectric ordering and the distinct splitting emerges in the libration, which dynamically modulates the O(2)-O'(2) distance of the dimer. The PAPT(lib) associated with the libration is confirmed to be a driving force of the AF ordering.

NMR and NQR studies on transition-metal arsenide superconductors LaRu2As2, KCa2Fe4As4F2, and A2Cr3As3**Project supported by the National Natural Science Foundation of China (Grant Nos. 11674377, 11634015, and 11974405), the National Key R&D Program of China (Grant Nos. 2017YFA0302904 and 2016YFA0300502), and J. Y. also acknowledges support by the Youth Innovation Promotion Association of Chinese Academy of Sciences.

We report 75As-nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements on transition-metal arsenides LaRu2As 2, KCa2Fe4As4F2, and A2Cr3As3. In the superconducting state of LaRu2As2, a Hebel–Slichter coherence peak is found in the temperature dependence of the spin-lattice relaxation rate 1/T1 just below Tc, which indicates that LaRu2As2 is a full-gap superperconducor. For KCa2Fe4As4F2, antiferromagnetic spin fluctuations are observed in the normal state. We further find that the anisotropy rate is small and temperature independent, implying that the low energy spin fluctuations are isotropic in spin space. Our results indicate that KCa2Fe4As4F2 is a moderately overdoped iron-arsenide high-temperature superconductor with a stoichiometric composition. For A2Cr3As3 (A = Na, K, Rb, Cs), we calculate the electric field gradient by first-principle method and assign the 75As-NQR peaks to two crystallographically different As sites, paving the way for further NMR investigation.

Nuclear spin relaxation rate near the disorder-driven quantum critical point in Weyl fermion systems

Disorder such as impurities and dislocations in Weyl semimetals (SMs) drives a quantum critical point (QCP) where the density of states at the Weyl point gains a non-zero value. Near the QCP, the asymptotic low energy singularities of physical quantities are controlled by the critical exponents $\nu$ and $z$. The nuclear spin-lattice relaxation rate, which originates from the hyperfine coupling between a nuclear spin and long-range orbital currents in Weyl fermion systems, shows intriguing critical behavior. Based on the self-consistent Born approximation for impurities, we study the nuclear spin-lattice relaxation rate $1/T_1$ due to the orbital currents in disordered Weyl SMs. We find that $(T_1T)^{-1}\sim E^{2/z}$ at the QCP where $E$ is the maximum of temperature $T$ and chemical potential $\mu(T)$ relative to the Weyl point. This scaling behavior of $(T_1T)^{-1}$ is also confirmed by the self-consistent $T$-matrix approximation, where a remarkable temperature dependence of $\mu(T)$ could play an important role. We hope these results of $(T_1T)^{-1}$ will serve as an impetus for exploration of the disorder-driven quantum criticality in Weyl materials.

7Li NMR spectra and spin-lattice relaxation in lithium heptagermanate single crystal

7Li NMR spectra and spin-lattice relaxation in Li2Ge7O15 single crystal have been analyzed. It is shown that the NMR spectrum consists of quadrupolar triplets from 7Li (I = 3/2) nuclei located in structurally nonequivalent Li(1) and Li(2) sites (T = 300 K). On heating the quadrupolar splitting decreases as a result of thermal vibrations of 7Li quadrupolar axes whereas NMR lines narrow due to translational motion of lithium ions. Measurements of the spin-lattice relaxation rate T1−1 give information about the time scale and the activation energy of lithium ions motion. The results of NMR studies are compared with findings from electrical conductivity measurements.

NMR-based gap behavior related to the quantum size effect

We conducted$^{195}$Pt-nuclear magnetic resonance measurements on various-diameter Pt nanoparticles coated with polyvinylpyrrolidone in order to detect the quantum size effect and the discrete energy levels in the electron density of states, both of which were predicted by Kubo more than 50 years ago. We succeeded in separating the signals arising from the surface and interior regions and found that the nuclear spin-lattice relaxation rates in both regions show the metallic behavior at high temperatures. Surprisingly, the magnetic fluctuations in both regions exhibited anomalous behavior below the same temperature $T^*$, which points to a clear size dependence and is well scaled with $\delta_\mathrm{Kubo}$. These results suggest that a size-tunable metal-insulator transition occurs in the Pt nanoparticles as a result of the Kubo effect.

105Pd NMR and NQR study of the cubic heavy fermion system Ce3Pd20Si6

We report 105Pd nuclear magnetic resonance (NMR) and nuclear quadrupolar resonance (NQR) measurements on a single crystal of Ce3Pd20Si6, where antiferroquadrupolar and antiferromagnetic orders develop at low temperature. From the analysis of NQR and NMR spectra, we have determined the electric field gradient (EFG) tensors and the anisotropic Knight shift (K) components for both inequivalent Pd sites—Pd(32f) and Pd(48h). The observed EFG values are in excellent agreement with our state-of-the-art density functional theory calculations. The principal values of the quadrupolar coupling are MHz and MHz, for the Pd(32f) and Pd(48h) sites, respectively, which is large compared to the Larmor frequency defined by the gyromagnetic constant MHz/T for 105Pd. Therefore, the complete knowledge of K and the EFG tensors is crucial to establish the correspondence between NMR spectra and crystallographic sites, which is needed for a complete analysis of the magnetic structure, static spin susceptibility, and the spin-lattice relaxation rate data and a better understanding of the groundstate of Ce3Pd20Si6.

NMR study of defect-induced magnetism in methylammonium lead iodide perovskite

In organic-inorganic perovskite semiconductor methylammonium lead iodide the occurrence of magnetism has been confirmed from magnetization and $^{1}\mathrm{H}$ nuclear magnetic resonance (NMR) measurements. From room temperature down to 4 K, the magnetization is a combination of weak ferromagnetism and paramagnetism. $^{1}\mathrm{H}$ NMR spectra at low temperatures also reveal two components, one with a small chemical shift characteristic of $^{1}\mathrm{H}$ resonance in nonmetals, and the other with a much larger shift of $\ensuremath{\sim}\ensuremath{-}100$ ppm that is ascribed to the ferromagnetism of the material. The analysis of NMR spectra as well as that of $^{1}\mathrm{H}$ spin-lattice relaxation rate ($1/{T}_{1}$) indicates that disorder produces an inhomogeneous distribution of magnetic moments that order ferromagnetically where they are dense enough and otherwise behave as random paramagnetic impurities. It is shown that magnetism arises from iodine and lead vacancies present in the orthorhombic and cubic crystal phases of the material.

Effective-Field Approach to Magnetic Properties of Spin-1 System in XXZ Model with Single-Ion Uniaxial Anisotropy

In the XXZ Heisenberg model with the positive single-ion uniaxial anisotropy D, magnetic properties of the spin-1 system are studied by the one-site effective-field theory, which takes account of the effect of on-site spin fluctuations in the direction of the magnetization, neglected in the mean-field approximation. At temperatures above the transition point, a spin susceptibility is generally derived, and in the temperature range much above the exchange coupling constants and D, the susceptibility is shown to agree with that given by the mean-field approximation, leading to the correct Curie–Weiss law in accordance with the result in the high-temperature expansion. In the present case where the easy-plane of magnetization is xy-plane, the critical exchange coupling constant for the ferromagnetic order is Jxc/D = 0.182, which is larger than the value by the mean-field approximation 0.125 due to the effect of quantum-spin fluctuations. Characteristic behaviors of the susceptibility in the absence of the ferromagnetic order are explored in detail. The results are applied to an analysis for spin–lattice relaxation rate \(T_{1}^{ - 1}\) in Li9V3(P2O7)3(PO4)2, which is shown to be definitely linear in the square root of the susceptibility in the x-direction, \(T_{1}^{ - 1} \propto \chi _{\text{s}}^{x}{}^{1/2}\), consistent with the theory by Moriya.

Unified phase diagram of F-doped LaFeAsO by means of NMR and NQR parameters

We present $^{75}$As Nuclear Magnetic and Quadrupole Resonance results (NMR, NQR) on a new set of LaFeAsO$_{1-x}$F$_x$ polycrystalline samples. Improved synthesis conditions led to more homogenized samples with better control of the fluorine content. The structural$\equiv$nematic, magnetic, and superconducting transition temperatures have been determined by NMR spin-lattice relaxation rate and AC susceptibility measurements. The so-determined phase diagram deviates from the published one especially for low F-doping concentrations. However, if the doping level is determined from the NQR spectra, both phase diagrams can be reconciled. The absence of bulk coexistence of magnetism and superconductivity and a nanoscale separation into low-doping-like and high-doping-like regions have been confirmed. Additional frequency dependent intensity, spin-spin, and spin-lattice relaxation rate measurements on underdoped samples at the boundary of magnetism and superconductivity indicate that orthorhombicity and magnetism originate from the low-doping-like regions, and superconductivity develops at first in the high-doping-like regions.

Nuclear spin-lattice relaxation rate in noncentrosymmetric superconductors Y2C3

For a noncentrosymmetric superconductor such as Y2C3, we consider a parity-mixing model composed of spin-singlet s-wave and spin-triplet f-wave pairing components. The d-vector in f-wave state is chosen to be parallel to the Dresselhaus asymmetric spin-orbit coupling vector. It is found that, the quasiparticle excitation spectrum exhibits distinct nodal structure as a consequence of parity-mixing. We demonstrate particularly that such a model can qualitatively account for the existing experimental results of the temperature dependence of the nuclear spin-lattice relaxation rate T1−1 in Y2C3.

Proton dynamics in antiferroelectric CsH3(SeO3)2 single crystal investigated by 1H NMR measurements

1H nuclear magnetic resonance (NMR) measurements have been performed to study the proton dynamics associated with the antiferroelectric transition of a hydrogen-bonded single crystal of CsH3(SeO3)2. Herein, 1H NMR spectrum, shift, linewidth, and spin-lattice relaxation rate 1/T1 are measured in the temperature range of 80–296 K with the c-axis parallel to a magnetic field of ~4.85 T. The spectrum exhibits a composite structure with two narrow peaks at 296 K; at a low temperature, this structure evolves into a single broad shape with three humps. This complex shape and evolution are deconvoluted into five or six components based on the number of inequivalent and disordered hydrogen sites. By estimating the chemical shift and linewidth for each proton site, we identify all peaks. The spin-lattice relaxation recovery exhibits a double-exponential behavior with two relaxation times, short T1S and extremely large T1L. Both T1S and T1L follow Arrhenius behavior. From the respective 1/T1(T), the activation energies for proton motion are measured to be small: 1.16 ± 0.1 and 0.83 ± 0.06 kJ/mol for T1S and T1L, respectively. While the static NMR data, chemical shift and linewidth, show no evidence for the transition, the dynamic data 1/T1L highlights a clear increase across TN = 145 K, which is possibly a signature of the transition.

Approaching itinerant magnetic quantum criticality through a Hund's coupling induced electronic crossover in the YFe2Ge2 superconductor

Here, by conducting a systematic $^{89}$Y NMR study, we explore the nature of the magnetic ground state in a newly discovered iron-based superconductor YFe$_2$Ge$_2$. An incoherent-to-coherent crossover due to the Hund's coupling induced electronic correlation is revealed below the crossover temperature $T^*\sim 75\pm15\,\mathrm{K}$. During the electronic crossover, both the Knight shift ($K$) and the bulk magnetic susceptibility ($\chi$) exhibit a similar nonmonotonic temperature dependence, and a so-called Knight shift anomaly is also revealed by a careful $K$-$\chi$ analysis. Such an electronic crossover has been also observed in heavily hole-doped pnictide superconductors \emph{A}Fe$_2$As$_2$ (\emph{A} = K, Rb, and Cs), which is ascribed to the Hund's coupling induced electronic correlation. Below $T^*$, the spin-lattice relaxation rate divided by temperature $(1/T_1T)$ shows a similar suppression as the Knight shift, suggesting the absence of critical spin fluctuations. This seems to be in conflict with a predicted magnetic quantum critical point (QCP) near this system. However, considering a $\mathbf{q}$-dependent "filter" effect on the transferred hyperfine field, a predominant spin fluctuation with A-type correlation would be perfectly filtered out at $^{89}$Y sites, which is consistent with the recent inelastic neutron scattering results. Therefore, our results confirm that, through a Hund's coupling induced electronic crossover, the magnetic ground state of YFe$_2$Ge$_2$ becomes close to an itinerant magnetic QCP with A-type spin fluctuations. In addition, the possible superconducting pairing due to spin fluctuations is also discussed.

Identification of Binding Epitopes of a Fluorinated Compound Bound to Proteins Using 1H and 19F NMR Spectroscopy.

1H/19F NMR-based screening methods were applied to a human serum albumin-fleroxacin complex. Fleroxacin contains three fluorine atoms in a molecule, which is suitable as a model fluorinated compound for NMR analysis with 1H and 19F detection. The 19F{1H} and 1H{1H} saturation transfer difference spectra were acquired and the 1H/19F spin-lattice relaxation rates were measured with and without any selective irradiation of protein resonance to identify the binding epitopes of fleroxacin. Because several 1H signals of fleroxacin resonated close to water, its precise signal intensities were unavailable. The 19F NMR-based screening methods successfully provide complementary information, indicating its importance in the analysis of fluorinated compounds.

Impact of disorder on dynamics and ordering in the honeycomb-lattice iridate Na2IrO3

Kitaev's honeycomb spin-liquid model and its proposed realization in materials such as $\alpha$-RuCl$_3$, Li$_2$IrO$_3$ and Na$_2$IrO$_3$ continue to present open questions about how the dynamics of a spin-liquid are modified in the presence of non-Kitaev interactions as well as the presence of inhomogeneities. Here we use $^{23}$Na nuclear magnetic resonance to probe both static and dynamical magnetic properties in single crystal Na$_2$IrO$_3$. We find that the NMR shift follows the bulk susceptibility above 30 K but deviates from it below; moreover below $T_N$ the spectra show a broad distribution of internal magnetic fields. Both of these results provide evidence for inequivalent magnetic sites at low temperature, suggesting inhomogeneities are important for the magnetism. The spin-lattice relaxation rate is isotropic and diverges at $T_N$, suggesting that the Kitaev cubic axes may control the critical quantum spin fluctuations. In the ordered state, we observe gapless excitations, which may arise from site substitution, emergent defects from milder disorder, or possibly be associated with nearby quantum paramagnetic states distinct from the Kitaev spin liquid.

Effect of Cations on Interlayer Water Dynamics in Cation-Exchanged Montmorillonites Studied by Nuclear Magnetic Resonance and X-ray Diffraction Techniques

To ensure the safety of geological disposal of radioactive wastes, understanding the migration behavior of radioactive species in montmorillonite clays has become increasingly important. However, there are still many indeterminate aspects about the influence of cation species and humidity on the interlayer water dynamics and swelling properties of montmorillonite clays. In this work, by using XRD and 1H-NMR spin-lattice relaxation rate (1/T1) techniques, we aimed to clarify the relation between water layer thickness and molecular dynamics in various cation-exchanged montmorillonites (Mn+-MMTs; Mn+ = Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, La3+, Sm3+, and Lu3+) in the temperature range of -40 °C to 50 °C. XRD measurements showed that layer thickness in Mn+-MMTs increased with increasing hydrated water according to the order of structure-breaking chaotropic K+, Rb+, Cs+ ions, structure-making kosmotropic and borderline Li+, Na+, Ba2+ ions, divalent ions, and trivalent lanthanide ions. It was found t...