Showing papers on "Nuclear quadrupole resonance published in 2023"

Commensurate-to-incommensurate transition of charge-density-wave order and a possible quantum critical point in pressurized kagome metal CsV_3Sb_5

Abstract: Clarifying the interplay between charge density waves (CDWs) and superconductivity is important in the kagome metal CsV$_3$Sb$_5$, and pressure ($P$) can play a crucial role. Here, we present $^{121/123}$Sb nuclear quadrupole resonance (NQR) measurements under hydrostatic pressures up to 2.43 GPa in CsV$_3$Sb$_5$ single crystals. We demonstrate that the CDW gradually changes from a commensurate modulation with a star-of-David (SoD) pattern to an incommensurate one with a superimposed SoD and Tri-hexagonal (TrH) pattern stacking along the $c$-axis. Moreover, the linewidth $\delta u$ of $^{121/123}$Sb-NQR spectra increases with cooling down to $T_{\rm CDW}$, indicating the appearance of a short-range CDW order due to CDW fluctuations pinned by quenched disorders. The $\delta u$ shows a Curie-Weiss temperature dependence and tends to diverge at $P_{\rm c} \sim$ 1.9 GPa, suggesting that a CDW quantum critical point (QCP) exists at $P_{\rm c}$ where $T_{\rm c}$ shows the maximum. For $P > P_{\rm c}$, spin fluctuations are enhanced when the CDW is suppressed. Our results suggest that the maximal $T_{\rm c}$ at $P_{\rm c} \sim$ 1.9 GPa is related to the CDW QCP and the presence of spin fluctuations prevent the $T_{\rm c}$ from a rapid decrease otherwise after the CDW is completely suppressed.

Symmetry Analysis of Zero-Field Antiferroquadrupole Order in CeB6: Extremely Low-Frequency 11B-NQR Study

Abstract: The zero-field state in the antiferroquadrupole (AFQ) ordered phase of CeB6 has been investigated by a 11B-nuclear quadrupole resonance (NQR) measurement that is sensitive to changes in local charge distribution. In order to achieve this experiment, we have improved our low-frequency NQR techniques, so that the 11B-NQR spectrum has been successfully observed at an NQR frequency νQ ∼ 560 kHz, exceptionally low frequency among direct NQR measurements on strongly correlated electron systems. The temperature dependence of the NQR spectrum reveals that νQ rapidly decreases just below AFQ ordering temperature TQ = 3.3 K, while the spectral shape does not show any sign of site splitting below TQ. The latter is incompatible with the theoretical prediction based on the Oxy-type AFQ order, suggesting that the ordered state in the zero-field region differs from that in the nonzero-field region. Some new possible interpretations to explain the obtained results are proposed.

Calorimetric measurement of nuclear spin-lattice relaxation rate in metals

Abstract: 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.

Zero field magnetic resonance spectroscopy based on Nitrogen-vacancy centers

Abstract: We propose a scheme to have zero field magnetic resonance spectroscopy based on a nitrogen-vacancy center and investigate the new applications in which magnetic bias field might disturb the system under investigation. Continual driving with circularly polarized microwave fields is used to selectively address one spin state. The proposed method is applied for single molecule spectroscopy, such as nuclear quadrupole resonance spectroscopy of a $^{11}$B nuclear spin and the detection of the distance of two hydrogen nuclei in a water molecule. Our work extends applications of NV centers as a nanoscale molecule spectroscopy in the zero field regime.

Nuclear Magnetic Resonance (NMR), Electron Spin or Paramagnetic Resonance (ESR/EPR) and Nuclear Quadrupole Resonance (NQR) Spectroscopy

Abstract: This chapter is concerned with three types of resonance spectroscopy, divided into three parts, namely nuclear magnetic resonance (NMR), electron spin resonance (ESR) and nuclear quadrupole resonance (NQR) spectroscopy. In NMR spectroscopy, along with the experimental arrangement, the principle is explained with the help of several examples of NMR spectra. Explanation-based discussion has been given for the relaxation mechanisms, and the methods for the determination of their decay times are described. Bloch theory has been presented. Besides these, analytical discussions on the high-resolution NMR spectra (with several examples), solid-state NMR spectra and magic angle spinning are also described. A critical view of the process of nuclear magnetic resonance imaging (MRI) is given. In the second part, the principle and the experimental technique of ESR spectroscopy have been described at the beginning. Features of the hyperfine and the superhyperfine effects on the ESR spectra have also been presented with several examples. The effect of anisotropy on the ESR spectra and on their hyperfine coupling has been discussed. The characteristic features of ESR spectra of several transition metals have been critically investigated. In NQR spectroscopy, the theory of the process is given in details. On the basis of the theory, the NQR spectra of axially symmetric and non-axially symmetric systems with spin half and spin one nuclei have been discussed.

Elucidating the Role of Noncovalent Interactions in Favipiravir, a Drug Active against Various Human RNA Viruses; a 1H-14N NQDR/Periodic DFT/QTAIM/RDS/3D Hirshfeld Surfaces Combined Study

Abstract: Favipiravir (6-fluoro-3-hydroxypyrazine-2-carboxamide, FPV), an active pharmaceutical component of the drug discovered and registered in March 2014 in Japan under the name Avigan, with an indication for pandemic influenza, has been studied. The study of this compound was prompted by the idea that effective processes of recognition and binding of FPV to the nucleic acid are affected predominantly by the propensity to form intra- and intermolecular interactions. Three nuclear quadrupole resonance experimental techniques, namely 1H-14N cross-relaxation, multiple frequency sweeps, and two-frequency irradiation, followed by solid-state computational modelling (density functional theory supplemented by the quantum theory of atoms in molecules, 3D Hirshfeld Surfaces, and reduced density gradient) approaches were applied. The complete NQR spectrum consisting of nine lines indicating the presence of three chemically inequivalent nitrogen sites in the FPV molecule was detected, and the assignment of lines to particular sites was performed. The description of the nearest vicinity of all three nitrogen atoms was used to characterize the nature of the intermolecular interactions from the perspective of the local single atoms and to draw some conclusions on the nature of the interactions required for effective recognition and binding. The propensity to form the electrostatic N−H···O, N−H···N, and C−H···O intermolecular hydrogen bonds competitive with two intramolecular hydrogen bonds, strong O−H···O and very weak N−H···N, closing the 5-member ring and stiffening the structure, as well as π···π and F···F dispersive interactions, were analysed in detail. The hypothesis regarding the similarity of the interaction pattern in the solid and the RNA template was verified. It was discovered that the -NH2 group in the crystal participates in intermolecular hydrogen bonds N–H···N and N–H···O, in the precatalytic state only in N–H···O, while in the active state in N–H···N and N–H···O hydrogen bonds, which is of importance to link FVP to the RNA template. Our study elucidates the binding modes of FVP (in crystal, precatalytic, and active forms) in detail and should guide the design of more potent analogues targeting SARS-CoV-2. Strong direct binding of FVP-RTP to both the active site and cofactor discovered by us suggests a possible alternative, allosteric mechanism of FVP action, which may explain the scattering of the results of clinical trials or the synergistic effect observed in combined treatment against SARS-CoV-2.

A sulfur-33 Nuclear Quadrupole Resonance Study of 33 S2 -labeled L-Cystine.

Abstract: The sulfur electric-field-gradient (EFG) tensor for a disulfide bond in 33 S2 -labeled L-cystine has been investigated by 33 S nuclear quadrupole resonance (NQR). 33 S2 -labeled L-cystine is synthesized by introduction of disulfide ions prepared from elemental 33 S-sulfur into an amino acid derivative, the side chain of which is iodinated. In its NQR spectrum, sharp single peaks are observed at between 24.63 and 24.90 MHz in the temperature range from 80 to 298 K. The two-dimensional nutation echo 33 S NQR experiment is carried out at 160 K, and the quadrupole coupling constant, CQ , and the asymmetric parameter, ηQ , are obtained to be 46.9(9) MHz and 0.6(1), respectively. The calculated 33 S EFG tensor components with respect to the molecular frame is briefly discussed.

Novel Approach to the Best-Known Antiferroquadrupolar Material

Abstract: Nuclear quadrupole resonance (NQR) experiments were performed on CeB6 in an extremely-low-frequency range. These experiments revealed a clear anomaly in the NQR frequency at the antiferroquadrupolar transition of f electrons, albeit with no line splitting or broadening. The results pose a new question regarding the most prominent multipolar materials studied for over 40 years.

3D to 0D cesium lead bromide: A 79/81Br NMR, NQR and theoretical investigation.

Abstract: Inorganic metal halides offer unprecedented tunability through elemental variation of simple three-element compositions, but can exhibit complicated phase behaviour, degradation, and microscopic phenomena (disorder/dynamics) that play an integral role for the bulk-level chemical and physical properties of these materials. Understanding the halogen chemical environment in such materials is crucial to addressing many of the concerns regarding implementing these materials in commercial applications. In this study, a combined solid-state nuclear magnetic resonance, nuclear quadrupole resonance and quantum chemical computation approach is used to interrogate the Br chemical environment in a series of related inorganic lead bromide materials: CsPbBr3, CsPb2Br5, and Cs4PbBr6. The quadrupole coupling constants (CQ) were determined to range from 61 to 114 MHz for 81Br, with CsPbBr3 exhibiting the largest measured CQ and Cs4PbBr6 the smallest. GIPAW DFT was shown to be an excellent pre-screening tool for estimating the EFG of Br materials and can increase experimental efficiency by providing good starting estimates for acquisition. Finally, the combination of theory and experiment to inform the best methods for expanding further to the other quadrupolar halogens is discussed.

Microscopic characterization of the magnetic properties of the itinerant antiferromagnet La2Ni7 by 139La NMR/NQR measurements

Abstract: 139La nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements have been performed to investigate the magnetic properties of the itinerant magnet La2Ni7 which shows a series of antiferromagnetic (AFM) phase transitions at $T_{N1}$=61 K, $T_{N2}$=56 K, and $T_{N3}$=42 K under zero magnetic field. Two distinct La NMR signals were observed due to the two crystallographically inequivalent La sites in La2Ni7 (La1 and La2 in the La2Ni4 and the LaNi5 sub-units of the La2Ni7 unit cell, respectively). From the 139La NQR spectrum in the AFM state below $T_{N3}$, the AFM state was revealed to be a commensurate state where Ni ordered moments align along the crystalline c axis. Owing to the two different La sites, we were able to estimate the average values of the Ni ordered moments ($\sim$0.07-0.08 $\mu_{B}$/Ni and $\sim$0.17$\mu_{B}$/Ni around La1 and La2, respectively) from 139La NMR spectrum measurements in the AFM state below $T_{N3}$, suggesting a non-uniform distribution of the Ni-ordered moments in the AFM state. In contrast, a more uniform distribution of the Ni-ordered moments in the saturated paramagnetic state induced by the application of high magnetic fields is observed. The temperature dependence of the sublattice magnetization measured by the internal field at the La2 site in the AFM state was reproduced by a local moment model better than the self-consistent renormalization (SCR) theory for weak itinerant antiferromagnets. Given the small Ni-ordered moments in the magnetically ordered state, our results suggest that La2Ni7 has characteristics of both itinerant and localized natures in its magnetism. With this in mind, it is noteworthy that the temperature dependence of nuclear spin-relaxation rates in the paramagnetic state above $T_{N1}$ measured at zero magnetic field can be explained qualitatively by both the SCR theory and the local-moment model.

Commensurate-to-incommensurate transition of charge-density-wave order and a possible quantum critical point in pressurized kagome metal CsV$_3$Sb$_5$

Abstract: Clarifying the interplay between charge density waves (CDWs) and superconductivity is important in the kagome metal CsV$_3$Sb$_5$, and pressure ($P$) can play a crucial role. Here, we present $^{121/123}$Sb nuclear quadrupole resonance (NQR) measurements under hydrostatic pressures up to 2.43 GPa in CsV$_3$Sb$_5$ single crystals. We demonstrate that the CDW gradually changes from a commensurate modulation with a star-of-David (SoD) pattern to an incommensurate one with a superimposed SoD and Tri-hexagonal (TrH) pattern stacking along the $c$-axis. Moreover, the linewidth $\delta u$ of $^{121/123}$Sb-NQR spectra increases with cooling down to $T_{\rm CDW}$, indicating the appearance of a short-range CDW order due to CDW fluctuations pinned by quenched disorders. The $\delta u$ shows a Curie-Weiss temperature dependence and tends to diverge at $P_{\rm c} \sim$ 1.9 GPa, suggesting that a CDW quantum critical point (QCP) exists at $P_{\rm c}$ where $T_{\rm c}$ shows the maximum. For $P > P_{\rm c}$, spin fluctuations are enhanced when the CDW is suppressed. Our results suggest that the maximal $T_{\rm c}$ at $P_{\rm c} \sim$ 1.9 GPa is related to the CDW QCP and the presence of spin fluctuations prevent the $T_{\rm c}$ from a rapid decrease otherwise after the CDW is completely suppressed.

Theoretical Prediction of Nuclear Quadrupole Resonance Spectra of Aluminum, Bromine and Nitrogen Compounds via First Principles Calculations

Abstract: We study the interaction of the electric field gradient (EFG) and the nuclear quadrupole moment of 81Br,27Al, and 14N nuclei via ab initio quantum chemistry calculations. The primary goal is to predict the nuclear magnetic resonance (NMR) spectral parameters of interesting materials and assist in interpretation of their spectra. The calculations predict NMR spectral parameters for:

Calorimetric measurement of nuclear spin-lattice relaxation rate in metals

Abstract: 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.

Possible New State in CeB6 Uncovered by Extremely Low-Frequency Nuclear Quadrupole Resonance Experiments

Abstract: Extremely low-frequency nuclear quadrupole resonance analyses of CeB6, a prototypical antiferroquadrupole (AFQ) material, indicate the possible existence of a new state in the zero-field AFQ ordered phase.

Observation of multigap and coherence peak in the noncentrosymmetric superconductor CaPtAs: <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mmultiscripts><mml:mi>As</mml:mi><mml:mprescripts /><mml:none /><mml:mn>75</mml:mn></mml:mmultiscripts></mml:math> nuclear quadrupole resonance measurements

Abstract: 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.

Nuclear quadrupole resonance spectroscopy with a femtotesla diamond magnetometer

Abstract: Sensitive Radio-Frequency (RF) magnetometers that can detect oscillating magnetic fields at the femtotesla level are needed for demanding applications such as Nuclear Quadrupole Resonance (NQR) spectroscopy. RF magnetometers based on Nitrogen-Vacancy (NV) centers in diamond have been predicted to offer femtotesla sensitivity, but published experiments have largely been limited to the picotesla level. Here, we demonstrate a femtotesla RF magnetometer based on an NV-doped diamond membrane inserted between two ferrite flux concentrators. The device operates in bias magnetic fields of 2-10 microtesla and provides a ~300-fold amplitude enhancement within the diamond for RF magnetic fields in the 0.07-3.6 MHz range. The magnetometer's sensitivity is ~70 fT s^{1/2} at 0.35 MHz, and the noise floor decreases to below 2 fT after 1 hour of acquisition. We used this sensor to detect the 3.6 MHz NQR signal of 14N in sodium nitrite powder at room temperature. NQR signals are amplified by a resonant RF coil wrapped around the sample, allowing for higher signal-to-noise ratio detection. The diamond RF magnetometer's recovery time after a strong RF pulse is ~35 us, limited by the coil ring-down time. The sodium-nitrite NQR frequency shifts linearly with temperature as -1.00 +/- 0.02 kHz/K, the magnetization dephasing time is T2* = 887 +/- 51 us, and a spin-lock spin-echo pulse sequence extends the signal lifetime to 332 +/- 23 ms, all consistent with coil-based NQR studies. Our results expand the sensitivity frontier of diamond magnetometers to the femtotesla range, with potential applications in security, medical imaging, and materials science.

Efficient NMR measurement and data analysis supported by the Bayesian inference : The case of the heavy fermion compound YbCo2Zn20

Abstract: We propose a data-driven technique to infer microscopic physical quantities from nuclear magnetic resonance(NMR) spectra, in which the data size and quality required for the Bayesian inference are investigated. The $^{59}$Co-NMR measurement of YbCo$_2$Zn$_{20}$ single crystal generates complex spectra with 28 peaks. By exploiting the site symmetry in the crystal structure, the isotropic Knight shift $K_{iso}$ and nuclear quadrupole resonance(NQR) frequency $ u_Q$ were estimated to be $K_{iso} = 0.7822 \pm 0.0090 \%$, $ u_Q = 2.008 \pm 0.016$ MHz ( T = 20 K, H $\simeq$ 10.2 T) by analyzing only 30 data points from one spectrum. The estimation of $ u_Q$ is consistent with the precise value obtained in the NQR experiment. Our method can significantly reduce the measurement time and the computational cost of data analysis in NMR experiments.