Nuclear Magnetic Resonance Spin-lattice Relaxation Rate Research Articles

SrCu(OH)3Cl , an isolated equilateral triangle spin S=1/2 model system

We have investigated the magnetic ground state properties of the quantum spin trimer compound strontium hydroxy copper chloride SrCu(OH)3Cl using bulk magnetization, specific heat measurements, nuclear magnetic resonance (NMR), and electron spin resonance (ESR) spectroscopy. SrCu(OH)3Cl consists of layers with isolated Cu2+ triangles and hence provides an opportunity to understand the magnetic ground state of an isolated system of S = 1/2 arranged on an equilateral triangle. Although magnetization measurements do not exhibit a phase transition to a long-range ordered state down to T = 2 K, they reveal the characteristic behavior of isolated trimers with an exchange of J=154 K. The Curie-Weiss behavior changes around 50–80 K, as is also seen in the NMR spin-lattice relaxation rate. In zero magnetic field, our specific heat data establish a second-order phase transition to an antiferromagnetic ground state below T= 1.2 K. We have drawn a magnetic field-temperature (H−T) phase diagram based on the specific heat measurements. The ESR data show divergence of the linewidth at lower temperatures, which precedes the phase transition to an antiferromagnetic long-range ordered state with unconventional critical exponents. The temperature variation of the g-factor further confirms the antiferromagnetic phase transition and reflects the underlying magnetocrystalline anisotropy of the compound. Published by the American Physical Society 2024

Deformed spin- 12 square lattice in antiferromagnetic NaZnVOPO4(HPO4)

We report the structural and magnetic properties of a new spin-$\frac12$ antiferromagnet NaZnVOPO$_4$(HPO$_4$) studied via x-ray diffraction, magnetic susceptibility, high-field magnetization, specific heat, and $^{31}$P nuclear magnetic resonance (NMR) measurements, as well as density-functional band-structure calculations. While thermodynamic properties of this compound are well described by the $J_1-J_2$ square-lattice model, \textit{ab initio} calculations suggest a significant deformation of the spin lattice. From fits to the magnetic susceptibility we determine the averaged nearest-neighbor and second-neighbor exchange couplings of $\bar J_1\simeq -1.3$ K and $\bar J_2\simeq 5.6$ K, respectively. Experimental saturation field of 15.3\,T is consistent with these estimates if 20\% spatial anisotropy in $J_1$ is taken into account. Specific heat data signal the onset of a magnetic long-range order at $T_{\rm N} \simeq 2.1$ K, which is further supported by a sharp peak in the NMR spin-lattice relaxation rate. The NMR spectra mark the superposition of two P lines due to two noneqivalent P sites where the broad line with the strong hyperfine coupling and short $T_1$ is identified as the P(1) site located within the magnetic planes, while the narrow line with the weak hyperfine coupling and long $T_1$ is designated as the P(2) site located between the planes.

Breakdown of atomic spin-orbit coupling picture in an apparently isolated pseudo-one-dimensional iridate: Sr3NaIrO6

In the presence of strong atomic spin-orbit coupling (SOC), tending to the $j\text{\ensuremath{-}}j$ coupling limit, $5{d}^{4}$ iridates are speculated to possess a nonmagnetic ${J}_{\mathrm{eff}}=0$ singlet ground state from atomic consideration, which invariably gets masked due to different solid-state effects (e.g., hopping). Here, we try to probe the trueness of the atomic SOC-based proposal in an apparently one-dimensional system, ${\mathrm{Sr}}_{3}{\mathrm{NaIrO}}_{6}$, with well-separated ${\mathrm{Ir}}^{5+}$ $(5{d}^{4})$ ions. But all the detailed experimental as well as theoretical characterizations reveal that the ground state of ${\mathrm{Sr}}_{3}{\mathrm{NaIrO}}_{6}$ is not nonmagnetic. However, our combined dc susceptibility $\ensuremath{\chi}$, $^{23}\mathrm{Na}$ nuclear magnetic resonance (NMR), muon spin relaxation/rotation $(\ensuremath{\mu}\mathrm{SR})$, and heat capacity ${C}_{p}$ measurements clearly refute any sign of spin freezing or ordered magnetism among the ${\mathrm{Ir}}^{5+}$ moments due to geometrical exchange frustration, while in-depth zero-field and longitudinal field $\ensuremath{\mu}\mathrm{SR}$ investigations strongly point towards an inhomogeneous quantum spin liquid (QSL)-like ground state. In addition, the linear temperature dependence of both the NMR spin-lattice relaxation rate and the magnetic heat capacity at low temperatures suggest low-lying gapless spin excitations in the QSL phase of this material. Finally, we conclude that the effective SOC realized in ${d}^{4}$ iridates is unlikely to offer a ground state which will be consistent with a purely atomic $j\text{\ensuremath{-}}j$ coupling description.

Spin- 12 chain compound Ba2Cu2Te2P2O13 : Magnetization, specific heat, and local-probe NMR

We present synthesis and characterization of ${\mathrm{Ba}}_{2}{\mathrm{Cu}}_{2}{\mathrm{Te}}_{2}{\mathrm{P}}_{2}{\mathrm{O}}_{13}$ (BCTPO) via x-ray diffraction, magnetic susceptibility, heat capacity, and $^{31}\mathrm{P}$ nuclear magnetic resonance (NMR) measurements. BCTPO crystallizes in a monoclinic structure with ${\mathrm{Cu}}^{2+}$ ions forming coupled chains. In magnetization $M(T)$ measurements, a broad maximum is observed around 53 K. Upon the application of magnetic fields, a sharp anomaly evolves around 4 K in the heat capacity ${C}_{P}(T)$ data, indicative of long-range order, while it is absent in zero field. The $^{31}\mathrm{P}$ NMR line shift at about 93.954 kOe tracks the spin susceptibility, whereas the line broadening evidences the onset of magnetic order at about 4 K or lower. The inferred isotropic and axial components of the hyperfine coupling constant are ${A}_{hf}^{\mathrm{iso}}\ensuremath{\simeq}$ 3635 $\text{Oe}/{\ensuremath{\mu}}_{B}$ and ${A}_{hf}^{ax}\ensuremath{\simeq}$ 479 $\text{Oe}/{\ensuremath{\mu}}_{B}$, respectively. The $^{31}\mathrm{P}$ NMR spin-lattice relaxation rate $1/{T}_{1}$ shows a pronounced divergence for $T\ensuremath{\longrightarrow}0$. We assign this behavior to critical fluctuations on the verge of order.

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.

The spin-1/2 coupled tetramer system Ba(TiO) Cu4(PO4)4 probed by magnetization, specific heat, and 31P NMR

We present the synthesis and a detailed investigation of structural and magnetic properties of polycrystalline Ba(TiO) Cu4(PO4)4 (BTCPO) via X-ray diffraction, magnetic susceptibility, heat capacity, and 31P Nuclear Magnetic Resonance (NMR) measurements. BTCPO has a 2D layered structure with interlinked Cu4O12 tetramer units. A broad maximum is observed around 16.5 K in our magnetization data accompanied by a sharp anomaly around T = 9.5 K in the heat capacity. An anomaly at about T = 10 K is also found in the temperature dependence of the 31P NMR spin-lattice relaxation rate 1/T1. A power law behavior for the heat capacity as well as for the 31P 1/T1 below the ordering temperature could be obtained. The 31P NMR lineshape is asymmetric and the NMR shift tracks the bulk spin-susceptibility. We estimated the isotropic and axial components of the hyperfine coupling tensor to be as the Ahfiso⋍6794Oe/μB and Ahfax⋍818Oe/μB, respectively.

Structural and magnetic properties of a new cubic spinel LiRhMnO4

We report the structural and magnetic properties of a new system LiRhMnO$_{4}$ (LRMO) through x-ray diffraction, bulk magnetization, heat capacity and $^{7}$Li nuclear magnetic resonance (NMR) measurements. LRMO crystallizes in the cubic space group $\mathit{Fd}$$\bar{3}$$\mathit{m}$. From the DC susceptibility data, we obtained the Curie-Weiss temperature $\mathrm{\theta}_{\mathrm{CW}}$ = -26 K and Curie constant $\mathit{C}$ = 1.79 Kcm$^{3}$/mol suggesting antiferromagnetic correlations among the magnetic Mn$^{4+}$ ions with an effective spin $\mathit{S}$ = $\frac{3}{2}$. At $\mathit{H}$ = 50 Oe, the field cooled and zero-field cooled magnetizations bifurcate at a freezing temperature, $T_{f}$ = 4.45 K, which yields the frustration parameter $\mathit{f=\frac{\mid\theta_{CW}\mid}{T_{f}}}>$5. AC susceptibility, shows a cusp-like peak at around $T_{f}$, with the peak position shifting as a function of the driving frequency, confirming a spin-glass-like transition in LRMO. LRMO also shows typical spin-glass characteristics such as memory effect, aging effect and relaxation. In the heat capacity, there is no sharp anomaly down to 2 K indicative of long-range ordering. The field sweep $^{7}$Li NMR spectra show broadening with decreasing temperature without any spectral line shift. The $^{7}$Li NMR spin-lattice and spin-spin relaxation rates also show anomalies due to spin freezing near $T_{f}$.

Singlet ground state in the alternating spin- 12 chain compound NaVOAsO4

We present the synthesis and a detailed investigation of structural and magnetic properties of polycrystalline NaVOAsO$_4$ by means of x-ray diffraction, magnetization, electron spin resonance (ESR), and $^{75}$As nuclear magnetic resonance (NMR) measurements as well as density-functional band structure calculations. Temperature-dependent magnetic susceptibility, ESR intensity, and NMR line shift could be described well using an alternating spin-$1/2$ chain model with the exchange coupling $J/k_{\rm B}\simeq 52$ K and an alternation parameter $\alpha \simeq 0.65$. From the high-field magnetic isotherm measured at $T=1.5 $ K, the critical field of the gap closing is found to be $ H_{\rm c}\simeq 16$ T, which corresponds to the zero-field spin gap of $\Delta_0/k_{\rm B}\simeq 21.4$ K. Both NMR shift and spin-lattice relaxation rate show an activated behavior at low temperatures, further confirming the singlet ground state. The spin chains do not coincide with the structural chains, whereas the couplings between the spin chains are frustrated. Because of a relatively small spin gap, NaVOAsO$_4$ is a promising compound for further experimental studies under high magnetic fields.

Nuclear magnetic resonance investigation of the heavy fermion system Ce2CoAl7Ge4

We present nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements performed on single crystalline \ccag{}, a member of a recently discovered family of heavy fermion materials Ce$_2M$Al$_7$Ge$_4$ ($M$ = Co, Ir, Ni, or Pd). Previous measurements indicated a strong Kondo interaction as well as magnetic order below $T_M = 1.8$ K. Our NMR spectral measurements show that the Knight shift $K$ is proportional to the bulk magnetic susceptibility $\chi$ at high temperatures. A clear Knight shift anomaly ($K \not\propto \chi$) is observed at coherence temperatures $T^* \sim 17.5$ K for $H_0 \parallel \hat{c}$ and 10 K for $H_0 \parallel \hat{a}$ at the ${}^{59}$Co site, and $T^* \sim 12.5$ K at the ${}^{27}$Al(3) site for $H_0 \parallel \hat{a}$ characteristic of the heavy fermion nature of this compound. At high temperatures the ${}^{59}$Co NMR spin-lattice relaxation rate $T_1^{-1}$ is dominated by spin fluctuations of the 4$f$ local moments with a weak metallic background. The spin fluctuations probed by ${}^{59}$Co NMR are anisotropic and larger in the basal plane than in the $c$ direction. Furthermore, we find $(T_1TK)^{-1} \propto T^{-1/2}$ at the ${}^{59}$Co site as expected for a Kondo system for $T > T^*$ and $T> T_K$. ${}^{59}$Co NQR \slrr{} measurements at low temperatures indicate slowing down of spin fluctuations above the magnetic ordering temperature $T_M \sim 1.8$ K. A weak ferromagnetic character of fluctuations around $\mathbf{q}=0$ is evidenced by an increase of $\chi T$ versus $T$ above the magnetic ordering temperature. We also find good agreement between the observed and calculated electric field gradients at all observed sites.

Transport and NMR characteristics of the skutterudite-related compound Ca3Rh4Sn13

We report the electronic properties of the Yb3Rh4Sn13-type single crystalline Ca3Rh4Sn13 by means of the electrical resistivity, Hall coefficient, Seebeck coefficient, thermal conductivity, as well as 119Sn nuclear magnetic resonance (NMR) measurements. The negative sign of the Hall coefficient and Seebeck coefficient at low temperatures suggests that the n-type carriers dominate the electrical transport in Ca3Rh4Sn13, in contrast to the observations in Sr3Rh4Sn13 which has a p-type conduction. Such a finding indicates a significant difference in the electronic features between these two stannides. Furthermore, we analyzed the temperature-dependent 119Sn NMR spin-lattice relaxation rate for Ca3Rh4Sn13, (Sr0.7Ca0.3)3Rh4Sn13, and Sr3Rh4Sn13 to examine the change of the electronic Fermi-level density of states (DOS) in (Sr1-xCax)3Rh4Sn13. It indicates that the Sn 5s partial Fermi-level DOS enhances with increasing the Ca content, being consistent with the trend of the superconducting temperature. Since the total Fermi-level DOS usually obeys the same trend of the partial Fermi-level DOS, the NMR analysis provides microscopic evidence for the correlation between the electronic DOS and superconductivity of the (Sr1-xCax)3Rh4Sn13 system.

Semimetallic behavior in Heusler-type Ru2TaAl and thermoelectric performance improved by off-stoichiometry

We report a study of the temperature-dependent electrical resistivity, Seebeck coefficient, thermal conductivity, specific heat, and $^{27}\mathrm{Al}$ nuclear magnetic resonance (NMR) in Heusler-type ${\mathrm{Ru}}_{2}\mathrm{TaAl}$, to shed light on its semimetallic behavior. While the temperature dependence of the electrical resistivity exhibits semiconductorlike behavior, the analysis of low-temperature specific heat reveals a residual Fermi-level density of states (DOS). Both observations can be realized by means of a semimetallic scenario with the Fermi energy located in the pseudogap of the electronic DOS. The NMR Knight shift and spin-lattice relaxation rate show activated behavior at higher temperatures, attributing to the thermally excited carriers across a pseudogap in ${\mathrm{Ru}}_{2}\mathrm{TaAl}$. From the first-principles band structure calculations, we further provide a clear picture that an indirect overlap between electron and hole pockets is responsible for the formation of a pseudogap in the vicinity of the Fermi level of ${\mathrm{Ru}}_{2}\mathrm{TaAl}$. In addition, an effort for improving the thermoelectric performance of ${\mathrm{Ru}}_{2}\mathrm{TaAl}$ has been made by investigating the thermoelectric properties of ${\mathrm{Ru}}_{1.95}{\mathrm{Ta}}_{1.05}\mathrm{Al}$. We found significant enhancements in the electrical conductivity and Seebeck coefficient and marked reduction in the thermal conductivity via the off-stoichiometric approach. This leads to an increase in the figure-of-merit $ZT$ value from $6.1\ifmmode\times\else\texttimes\fi{}\phantom{\rule{0.16em}{0ex}}{10}^{\ensuremath{-}4}$ in ${\mathrm{Ru}}_{2}\mathrm{TaAl}$ to $3.4\ifmmode\times\else\texttimes\fi{}\phantom{\rule{0.16em}{0ex}}{10}^{\ensuremath{-}3}$ in ${\mathrm{Ru}}_{1.95}{\mathrm{Ta}}_{1.05}\mathrm{Al}$ at room temperature. In this respect, a further improvement of thermoelectric performance based on ${\mathrm{Ru}}_{2}\mathrm{TaAl}$ through other off-stoichiometric attempts is highly probable.

Solid-State NMR to Study Translational Li Ion Dynamics in Solids with Low-Dimensional Diffusion Pathways

Abstract Fundamental research on lithium ion dynamics in solids is important to develop functional materials for, e.g. sensors or energy storage systems. In many cases a comprehensive understanding is only possible if experimental data are compared with predictions from diffusion models. Nuclear magnetic resonance (NMR), besides other techniques such as mass tracer or conductivity measurements, is known as a versatile tool to investigate ion dynamics. Among the various time-domain NMR techniques, NMR relaxometry, in particular, serves not only to measure diffusion parameters, such as jump rates and activation energies, it is also useful to collect information on the dimensionality of the underlying diffusion process. The latter is possible if both the temperature and, even more important, the frequency dependence of the diffusion-induced relaxation rates of actually polycrystalline materials is analyzed. Here we present some recent systematic relaxometry case studies using model systems that exhibit spatially restricted Li ion diffusion. Whenever possible we compare our results with data from other techniques as well as current relaxation models developed for 2D and 1D diffusion. As an example, 2D ionic motion has been verified for the hexagonal form of LiBH4; in the high-temperature limit the diffusion-induced 7Li NMR spin-lattice relaxation rates follow a logarithmic frequency dependence as is expected from models introduced for 2D diffusion. A similar behavior has been found for Li x NbS2. In Li12Si7 a quasi-1D diffusion process seems to be present that is characterized by a square root frequency dependence and a temperature behavior of the 7Li NMR spin-lattice relaxation rates as predicted. Most likely, parts of the Li ions diffuse along the Si5 rings that form chains in the Zintl phase.

Ru2NbGa : A Heusler-type compound with semimetallic characteristics

The Heusler-type compound of ${\mathrm{Ru}}_{2}\mathrm{NbGa}$ has been successfully synthesized. X-ray analysis confirms that ${\mathrm{Ru}}_{2}\mathrm{NbGa}$ crystallizes in a cubic $L{2}_{1}$ structure. The electronic properties of ${\mathrm{Ru}}_{2}\mathrm{NbGa}$ have been characterized by means of the transport and nuclear magnetic resonance (NMR) measurements. The temperature dependence of the electrical resistivity exhibits a typical semimetallic behavior. The NMR spin-lattice relaxation rate shows activated behavior at higher temperatures, attributing to the thermally excited carriers across a pseudogap. We have also deduced a low Fermi-level density of states (DOS), being consistent with the semimetallic characteristic for ${\mathrm{Ru}}_{2}\mathrm{NbGa}$. In addition, we have performed first-principles total-energy calculations including ${G}_{0}{W}_{0}$ and $G{W}_{0}$ corrections for band gaps to investigate the electronic band structure of ${\mathrm{Ru}}_{2}\mathrm{NbGa}$. The calculated result reveals an indirect overlap between electron and hole pockets that leads to a residual DOS at the Fermi level, providing a consistent explanation for the experimental observations.

Enhanced superconducting transition temperature in hyper-interlayer-expanded FeSe despite the suppressed electronic nematic order and spin fluctuations

The superconducting critical temperature, $T_{\rm c}$, of FeSe can be dramatically enhanced by intercalation of a molecular spacer layer. Here we report on a $^{77}$Se, $^7$Li and $^1$H nuclear magnetic resonance (NMR) study of the powdered hyper-interlayer-expanded Li$_{x}($C$_2$H$_8$N$_2$)$_y$Fe$_{2-z}$Se$_2$ with a nearly optimal $T_{\rm c}=45$~K. The absence of any shift in the $^7$Li and $^1$H NMR spectra indicates a complete decoupling of interlayer units from the conduction electrons in FeSe layers, whereas nearly temperature-independent $^7$Li and $^1$H spin-lattice relaxation rates are consistent with the non-negligible concentration of Fe impurities present in the insulating interlayer space. On the other hand, strong temperature dependence of $^{77}$Se NMR shift and spin-lattice relaxation rate, $1/^{77}T_1$, is attributed to the hole-like bands close to the Fermi energy. $1/^{77}T_1$ shows no additional anisotropy that would account for the onset of electronic nematic order down to $T_{\rm c}$. Similarly, no enhancement in $1/^{77}T_1$ due to the spin fluctuations could be found in the normal state. Yet, a characteristic power-law dependence $1/^{77}T_1\propto T^{4.5}$ still comply with the Cooper pairing mediated by spin fluctuations.

Lattice distortion associated with Fermi-surface reconstruction inSr3Rh4Sn13

Superconducting ${\mathrm{Sr}}_{3}{\mathrm{Rh}}_{4}{\mathrm{Sn}}_{13}$ has been of current interest due to indications of a characteristic phase transition associated with structural distortions in its normal state. To further shed light on the nature of the phase transition, we performed a detailed study of single crystalline ${\mathrm{Sr}}_{3}{\mathrm{Rh}}_{4}{\mathrm{Sn}}_{13}$ by means of the thermal expansion, electrical resistivity, Hall coefficient, Seebeck coefficient, thermal conductivity, as well as $^{119}\mathrm{Sn}$ nuclear magnetic resonance (NMR) measurements, mainly focusing on the signatures around the phase transition temperature ${T}^{*}=137$ K. The phase transition has been characterized by marked features near ${T}^{*}$ in all measured physical quantities. In particular, the NMR characteristics provide microscopic evidence for the reduction in the electronic Fermi-level density of states (DOSs) below ${T}^{*}$. Based on the analysis of the $^{119}\mathrm{Sn}$ NMR spin-lattice relaxation rate, we clearly demonstrated that the Sn $5s$ partial Fermi-level DOS in ${\mathrm{Sr}}_{3}{\mathrm{Rh}}_{4}{\mathrm{Sn}}_{13}$ is reduced by 13% across the phase transition. In this respect, it points to the strong association between electronic and structural instability for the peculiar phase transition in ${\mathrm{Sr}}_{3}{\mathrm{Rh}}_{4}{\mathrm{Sn}}_{13}$.

Detection of a spin-triplet superconducting phase in oriented polycrystalline U(2)PtC(2) samples using ^(195)Pt nuclear magnetic resonance.

Nuclear magnetic resonance (NMR) measurements on the ^{195}Pt nucleus in an aligned powder of the moderately heavy-fermion material U_{2}PtC_{2} are consistent with spin-triplet pairing in its superconducting state. Across the superconducting transition temperature and to much lower temperatures, the NMR Knight shift is temperature independent for field both parallel and perpendicular to the tetragonal c axis, expected for triplet equal-spin pairing superconductivity. The NMR spin-lattice relaxation rate 1/T_{1}, in the normal state, exhibits characteristics of ferromagnetic fluctuations, compatible with an enhanced Wilson ratio. In the superconducting state, 1/T_{1} follows a power law with temperature without a coherence peak giving additional support that U_{2}PtC_{2} is an unconventional superconductor. Bulk measurements of the ac susceptibility and resistivity indicate that the upper critical field exceeds the Pauli limiting field for spin-singlet pairing and is near the orbital limiting field, an additional indication for spin-triplet pairing.

Li ion dynamics along the inner surfaces of layer-structured 2H-LixNbS2.

Layer-structured materials, such as graphite (LiCy) or Lix(Co,Ni,Mn)O2, are important electrode materials in current battery research that still relies on insertion materials. This is due to their excellent ability to reversibly accommodate small alkali ions such as Li(+) and Na(+). Despite of these applications, microscopic information on Li ion self-diffusion in transition metal sulfides are relatively rare. Here, we used (7)Li nuclear magnetic resonance (NMR) spectroscopy to study translational Li ion diffusion in hexagonal (2H) LixNbS2 (x = 0.3, 0.7, and 1) by means of variable-temperature NMR relaxometry. (7)Li spin-lattice relaxation rates and (7)Li NMR spectra were used to determine Li jump rates and activation barriers as a function of Li content. Hereby, NMR spin-lattice relaxation rates recorded with the spin-lock technique offered the possibility to study Li ion dynamics on both the short-range and long-range length scale. Information was extracted from complete diffusion-induced rate peaks that are obtained when the relaxation rate is plotted vs inverse temperature. The peak maximum of the three samples studied shifts toward higher temperatures with increasing Li content x in 2H-LixNbS2. Information on the dimensionality of the diffusion process was experimentally obtained by frequency dependent Rρ measurements carried out at T = 444 K, that is in the high-temperature regime of the rate peaks. A slight, but measurable frequency-dependence within this limit is found for all samples; it is in good agreement with predictions from relaxation models developed to approximate low-dimensional (2D) jump diffusion.

Ising-Type Ferromagnetic Ground State Driven by Anisotropic c–f Hybridization in CeRu2Al2B

The magnetic correlations between Ce 4f electrons and conduction electrons in the new tetragonal compound CeRu2Al2B have been investigated by 27Al nuclear magnetic resonance (NMR). The 27Al NMR spin–lattice relaxation rate 1/T1 exhibits a large magnetic anisotropy for field directions. Within a localized moment picture, the Ce 4f spin-fluctuation rates Γ|| for the c-axis and Γ⊥ for the c-plane are evaluated by taking account of the magnetic anisotropy. The relation of \(\Gamma _{\parallel } \gg \Gamma _{ \bot }\), which holds in the entire temperature range, indicates that the c–f hybridization between the ligand conduction electrons and the Ce 4f electrons with the \(\Gamma _{7}^{(1)}\) crystal electric field ground state is anisotropic. From the temperature dependence of Γ, it is found that the Kondo effect dominates the Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction at high temperatures, whereas below 60 K the RKKY interaction overcomes the Kondo effect and causes the magnetic order. These results in...

Strong Coupling of Rattling Phonon to Conduction Electrons in Semimetallic Type-I Clathrate Ba8Ga16Sn30

We report studies of 117,119Sn and 69,71Ga nuclear magnetic resonance (NMR) to investigate electron–phonon interactions due to the off-center rattling of Ba atoms in the semi-metallic type-I Ba8Ga16Sn30 clathrate with \(n\)-type charge carriers in the temperature range of 0.4–200 K. The Ga NMR spin–lattice relaxation rate has an anomalous enhancement at approximately 10 K, indicating that the Ba atoms exhibit thermal rattling motion in an anharmonic potential. From calculations using a two-phonon Raman process model for a one-dimensional anharmonic Hamiltonian within a quasi-harmonic approximation, significant broadening of the phonon lifetime and softening of the phonon frequency are found to be essential to reproduce the temperature dependence of the NMR spin–lattice relaxation rate. The characteristic energy of the renormalized phonon frequency ωr≈21 K was obtained for the rattling state, in agreement with the values estimated by heat capacity analysis and other techniques. These results point to strong coupling of the rattling phonon to conduction electrons in semimetallic type-I Ba8Ga16Sn30.

Evolution of the pseudogap in Sr1−xYxAl2Si2(x=0, 0.05, 0.1, and 0.15) probed viaAl27nuclear magnetic resonance

With the aim of providing microscopic information about the electronic characteristics of SrAl${}_{2}$Si${}_{2}$ and effects of chemical substitution on its pseudogap features, we carried out a study on Sr${}_{1\ensuremath{-}x}$Y${}_{x}$Al${}_{2}$Si${}_{2}$ ($x=$ 0, 0.05, 0.1, and 0.15) by means of $^{27}\mathrm{Al}$ nuclear magnetic resonance (NMR) spectroscopy. For stoichiometric SrAl${}_{2}$Si${}_{2}$, the temperature-dependent NMR Knight shift and spin-lattice relaxation rate are associated with a sharp feature in the electronic density of state within a pseudogap at around the Fermi level. On the other hand, the NMR observations for Y-substituted compounds exhibit ordinary metallic behavior, suggesting that the Fermi level has moved out of the pseudogap for these materials, resulting in the dominant Korringa process responsible for the observed relaxation rates.