Nuclear Quadrupole Resonance Spectra Research Articles

Structure of the kagome superconductor CsV3Sb5 in the charge density wave state

The structure of charge density wave states in AV$_3$Sb$_5$ (A = K, Rb, Cs) kagome superconductors remains elusive, with three possible $2a\times2a\times2c$ candidates: tri-hexagonal, star-of-David, and their mixture. In this study, we conducted a systematic first-principles investigation of the nuclear quadrupole resonance (NQR) and nuclear magnetic resonance (NMR) spectra for the $2a\times2a\times2c$ CsV$_3$Sb$_5$ structures. By comparing our simulations with experimental data, we have concluded that the NQR spectrum indicates the tri-hexagonal structure as the proper structure for CsV$_3$Sb$_5$ after its charge density wave phase transition. The NMR calculation results obtained from the tri-hexagonal structure are also consistent with the experimental data.

A novel adaptive noise canceling system for urea NQR spectrum analysis

Due to its practical ease of use and sufficiently high reliability, Nuclear Quadrupole Resonance (NQR) has largely been used in remote sensing-based detection of quadrupole nuclei, especially Nitrogen-containing materials. Since the received signal of free induction decay (FID) is inherently weak in this technique, the noise and the interference of the environment would dramatically impair the performance of the detecting systems. To handle such challenges, an adaptive noise canceling method was employed to improve the signal to noise and interference ratio (SNIR) in FID signals. FID signals, noise, and interference were received by the main antenna, while similar noise and interference would be received by the auxiliary antenna. The proposed system significantly reduced noise and interference through the digital noise and interference cancellation algorithm, pulse integration, averaging, and singular spectrum analysis (SSA). Urea powder was empirically analyzed outdoors, suggesting that the proposed adaptive noise and interference cancellation (ANIC) system, effectively suppressed noise and interference by 41.13 dB and amplified the FID signal by 53.36 dB. The strongest signal was detected at 2870.4 kHz.

A sulfur-33 nuclear quadrupole resonance study of 33 S2 -labeled L-cystine.

The sulfur electric-field-gradient 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 electric-field-gradient tensor components with respect to the molecular frame is briefly discussed.

Structural 130 K phase transition and emergence of a two-ion Kondo state in Ce2Rh2Ga explored by Ga69,71 nuclear quadrupole resonance

We have studied the microscopic magnetic properties, the nature of the 130-K phase transition, and the ground state in the recently synthesized compound Ce$_2$Rh$_2$Ga by use of $^{69,71}$Ga nuclear quadrupole resonance (NQR). The NQR spectra clearly show an unusual phase transition at $T_t$ $\sim$ 130 K yielding a splitting of the high-temperature single NQR line into two clearly resolved NQR lines, providing evidence for two crystallographically inequivalent Ga sites. The NQR frequencies are in good agreement with fully-relativistic calculations of the band structure. Our NQR results indicate the absence of magnetic or charge order down to 0.3 K. The temperature dependence of the spin-lattice relaxation rate, 1/$T_1$, shows three distinct regimes, with onset temperatures at $T_t$ and 2 K. The temperature-independent 1/$T_1$, observed between $T_t$ and 2 K, crosses over to a Korringa process, 1/$T_1$ $\propto$ $T$, below $\sim$ 2 K, which evidences a rare two-ion Kondo scenario: the system goes into a dense Kondo coherent state at 2.0 and 0.8 K for the two different Ga sites.

Hardware and program system for determination of authenticity of medicines by nuclear quadrupole resonance method

THE PURPOSE. Study the possibility of using a laboratory nuclear magnetic resonance console as a device for detecting counterfeit medicines. The problem of detecting counterfeit and counterfeit medicines is now very acute. Consider the potential of applying the nuclear quadrupole resonance radiospectroscopy method to determine the authenticity and quality of medicines by non-destructive means.ACTUALITY. The nuclear magnetic resonance method is included in the list of physico-chemical methods used in pharmacopia. The spectroscopy of nuclear quadrupole resonance, being similar in physical principles, has its advantages and advantages, which in general will strengthen the control of the authenticity and quality of medicines.METHODS. The theory of nuclear quadrupole resonance and features that allow to investigate medicinal preparations is resulted. The structural design of this hardware and software complex based on the Apollo Redstone nuclear quadrupole resonance spectrometer is described, its nodes are described, characteristics and parameters are given, a special attention is paid to the development of the sensor for the hardwarethe software complex and its coordination system with the spectrometer. Detailed description of its radio technical characteristics.RESULTS. The article shows the results of using the hardware software complex - measurements of spectra of nuclear quadrupole resonance for the drug paracetamol developed by various manufacturers, both Russia and foreign pharmaceutical companies. The possibility of measuring spectral characteristics directly in the package is shown. The necessary multi-pulse series of pulses, used in the measurement of spectral characteristics, are given. The possibility of receiving signals of spin echo with a good signal/noise ratio is shown, as well as the possibility of distinguishing different manufacturers' spectra of paracetamol according to the form of the release.CONCLUSION. The article shows a principal possibility of creation on the basis of this method of compact and portable devices for non-destructive identification of medicinal preparations.

I127 NQR spectra of a mixed layered semiconductor Pb0.9Co0.1I2

The results of studying the parameters of the nuclear quadrupole resonance spectra I127 of mixed layered semiconductors Pb1-xCoxI2 (0.0 ≤ x ≤ 0.1) were carried out. A change in the frequency and integrated intensity of the I127 NQR spectrum lines with a change in the Co+2 content was recorded. The possibility of the formation of nanocluster structures associated with the ferromagnetic influence of Co+2 ions is discussed. A deviation from the exponentiality of the spin-spin quadrupole relaxation time T2 is established, which indicates the heterogeneity of the distribution of nanocluster structures over the crystal volume.

Observation of Antiferromagnetic Order as Odd-Parity Multipoles inside the Superconducting Phase in CeRh_{2}As_{2}.

Spatial inversion symmetry in crystal structures is closely related to the superconducting (SC) and magnetic properties of materials. Recently, several theoretical proposals that predict various interesting phenomena caused by the breaking of the local inversion symmetry have been presented. However, experimental validation has not yet progressed owing to the lack of model materials. Here we present evidence for antiferromagnetic (AFM) order in CeRh_{2}As_{2} (SC transition temperature T_{SC}∼0.37 K), wherein the Ce site breaks the local inversion symmetry. The evidence is based on the observation of different extents of broadening of the nuclear quadrupole resonance spectrum at two crystallographically inequivalent As sites. This AFM ordering breaks the inversion symmetry of this system, resulting in the activation of an odd-parity magnetic multipole. Moreover, the onset of antiferromagnetism T_{N} within an SC phase, with T_{N}<T_{SC}, is quite unusual in systems wherein superconductivity coexists or competes with magnetism. Our observations show that CeRh_{2}As_{2} is a promising system to study how the absence of local inversion symmetry induces or influences unconventional magnetic and SC states, as well as their interaction.

Tri-hexagonal charge order in kagome metal CsV3Sb5 revealed by 121Sb nuclear quadrupole resonance

We report 121Sb nuclear quadrupole resonance (NQR) measurements on kagome superconductor CsV3Sb5 with T c = 2.5 K. 121Sb NQR spectra split after a charge density wave (CDW) transition at 94 K, which demonstrates a commensurate CDW state. The coexistence of the high temperature phase and the CDW phase between 91 K and 94 K manifests that it is a first order phase transition. The CDW order exhibits tri-hexagonal deformation with a lateral shift between the adjacent kagome layers, which is consistent with 2 × 2 × 2 superlattice modulation. The superconducting state coexists with CDW order and shows a conventional s-wave behavior in the bulk state.

Equatorial Electronic Structure in the Uranyl Ion: Cs2UO2Cl4 and Cs2UO2Br4.

Electric field gradient (EFG) tensors in the equatorial plane of the linear UO22+ ion have been measured by nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) experiments and computed by relativistic Kohn-Sham methods with and without environment embedding for Cs2UO2Cl4 and Cs2UO2Br4. This approach expands the possibilities for probing the electronic structure in uranyl complexes beyond the strongly covalent U-O bonds. The combined analyses find that one of the two largest principal EFG tensor components at the halogen sites points along the U-X bond (X = Cl, Br), and the second is parallel to the UO22+ ion; in Cs2UO2Cl4, the components are nearly equal in magnitude, whereas in Cs2UO2Br4, due to short-range bromide-cesium interactions, the equatorial component is dominant for one pair of Br sites and the axial component is larger for the second pair. The directions and relative magnitudes of the field gradient principal axes are found to be sensitive to the σ and π electron donation by the ligands and the model of the environment. Chlorine-35 NQR spectra of 235U-depleted and 235U-enriched Cs2UO2Cl4 exhibited no uranium-isotope-dependent shift, but the resonance of the depleted sample displayed a 58% broader line width.

S-Wave Superconductivity in Kagome Metal CsV3Sb5 Revealed by 121/123Sb NQR and 51V NMR MeasurementsSupported by the National Key Research and Development Program of China (Grant Nos. 2017YFA0302901, 2018YFE0202600, and 2016YFA0300504), the National Natural Science Foundation of China (Grant Nos. 11921004, 11634015, 11822412, and 11774423), the Beijing Natural Science Foundation (Grant No. Z200005), and the Strategic Priority Research Program and Key

We report 121/123Sb nuclear quadrupole resonance (NQR) and 51V nuclear magnetic resonance (NMR) measurements on kagome metal CsV3Sb5 with T c = 2.5 K. Both 51V NMR spectra and 121/123Sb NQR spectra split after a charge density wave (CDW) transition, which demonstrates a commensurate CDW state. The coexistence of the high temperature phase and the CDW phase between 91 K and 94 K manifests that it is a first-order phase transition. At low temperature, electric-field-gradient fluctuations diminish and magnetic fluctuations become dominant. Superconductivity emerges in the charge order state. Knight shift decreases and 1/T 1 T shows a Hebel–Slichter coherence peak just below T c, indicating that CsV3Sb5 is an s-wave superconductor.

Magnetically induced local lattice anomalies and low-frequency fluctuations in the Mott insulator La2O3Fe2Se2

We report a study of the Mott insulator ${\mathrm{La}}_{2}{\mathrm{O}}_{3}{\mathrm{Fe}}_{2}{\mathrm{Se}}_{2}$ by means of $^{139}\mathrm{La}$ nuclear quadrupole resonance (NQR). The NQR spectra evidence a single La site in the paramagnetic phase and two inequivalent La sites, La1 and La2, in the antiferromagnetic phase. These two sites are characterized by different quadrupole couplings, indicative of distinct lattice configurations segregated in domains. The dependence of the quadrupole coupling for La2 on temperature suggests that the structural distortion is driven by the magnetic order parameter. The nuclear transverse relaxation rate $1/{T}_{2}$ evidences fluctuations in the paramagnetic phase with characteristic frequencies well below the Heisenberg exchange frequency and likely associated with nematic fluctuations.

Successive magnetic transitions in the heavy-fermion superconductor Ce3PtIn11 studied by In115 nuclear quadrupole resonance

Nuclear quadrupole resonance (NQR) measurements were performed on the heavy fermion superconductor Ce3PtIn11 with Tc = 0.32 K. The temperature dependence of both spin-lattice relaxation rate 1/T1 and NQR spectra evidences the occurrence of two successive magnetic transitions with TN1 = 2.2 K and TN2 = 2.0 K. In successive magnetic transitions, even though the magnetic moment at the Ce(2) site plays a major role, the magnetic moment at the Ce(1) site also contributes to some extent. While a commensurate antiferromagnetic ordered state appears for TN2 < T < TN1, a partially incommensurate antiferromagnetic ordered state is suggested for T < TN2.

14N NQR Quantification of Sodium Nitrite and Urotropin Using Singular Spectrum Analysis (SSA) for Data Filtering

An 14N nuclear quadrupole resonance (NQR) spectroscopy method has been developed using the singular spectrum analysis (SSA) based on the principal components concept. For the first time, it was demonstrated that this method can be used as a low cost and non-destructive quantitative method for analyses of small amounts (< 100 mg) of nitrogen containing solids. NQR technique is closely related to nuclear magnetic resonance, but without need for external magnetic field, applicable to solid compounds with quadrupolar nuclei. The hardware configuration using a broadband matching transformer was constructed and advanced algorithms for quantitative analyses of 14N NQR spectra were outlined. The calibration curves obtained, after optimization, for the model compounds, sodium nitrite and urotropin (hexamethylenetetramine), showed excellent linearity up to 500 mg for sodium nitrite at a frequency of 4642 kHz and up to 300 mg for urotropin at a frequency of 3307 kHz. The limits of detection were determined as 41 mg and 24 mg, respectively. The experimental and analytical procedure was simple enough to allow relatively easy practical implementation.

Formation of PbMnI2 alloys: Structural, photoluminescence and nuclear quadrupole resonance studies

The structural, optical and nuclear quadrupole resonance (NQR) measurements of PbMnI2 alloys were carried out. This allows us to study the peculiarities of the formation of such alloys. It was found that pure PbI2 and Pb1-XMnXI2 crystals with X = (0.03–0.05) have the phase of 2H-polytype. It was shown that the investigated alloys can be presented as the crystal regions of Pb1-XMnXI2 solid solutions, embedded in PbI2 crystal matrix. These formations can be considered as platelet-shaped nanoparticles with a surface of several microns and a thickness of several tens of nm. Thus, PbMnI2 alloys are heterogeneous PbI2–PbMnI2 nanocomposites. The results of NQR spectra measurements also show that Mn2+ ions preferably replace Pb2+ ions in the crystalline layers. Here, the local deformations occur because the radii of Pb2+ and Mn2+ ions differ significantly. The broadening of optical and NQR lines is due to the presence of both these deformations and the crystal field fluctuations, which are characteristic of semiconductor solid solutions.

Suppression of ferromagnetic spin fluctuations in the filled skutterudite superconductor SrOs4As12 revealed by As75 NMR-NQR measurements

Motivated by the recent observation of ferromagnetic spin correlations in the filled skutterudite SrFe$_4$As$_{12}$ [Ding et al., Phys. Rev. B 98, 155149 (2018)], we have carried out $^{75}$As nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements to investigate the role of magnetic fluctuations in a newly discovered isostructural superconductor SrOs$_4$As$_{12}$ with a superconducting transition temperature of $T_{\rm c}$ $\sim$ 4.8 K. Knight shift $K$ determined by the NQR spectrum under a small magnetic field ($\le$ 0.5 T) is nearly independent of temperature, consistent with the temperature dependence of the magnetic susceptibility. The nuclear spin-lattice relaxation rate divided by temperature, 1/$T_1T$, is nearly independent of temperature above $\sim$ 50 K and increases slightly with decreasing temperature below the temperature. The temperature dependence is reasonably explained by a simple model where a flat band structure with a small ledge near the Fermi energy is assumed. By comparing the present NMR data with those in SrFe$_4$As$_{12}$, we found that the values of $|K|$ and $1/T_1T$ in SrOs$_4$As$_{12}$ are smaller than those in SrFe$_4$As$_{12}$, indicating no obvious ferromagnetic spin correlations in SrOs$_4$As$_{12}$. From the temperature dependence of 1/$T_1$ in the superconducting state, an $s$-wave superconductivity is realized.

Rapid Identification of Halogen Bonds in Co-Crystalline Powders via 127 I Nuclear Quadrupole Resonance Spectroscopy.

127 I nuclear quadrupole resonance (NQR) spectroscopy is established as a rapid and robust method to indicate the formation of iodine-nitrogen halogen bonds in co-crystalline powders. Once the relevant spectral frequency range has been established, diagnostic 127 I NQR spectra can be acquired in seconds. The method is demonstrated for a series of co-crystals of 1,4-diiodobenzene. Changes in the 127 I quadrupolar coupling constant (CQ ) by up to 74.4 MHz correlate with the length of the C-I donor covalent bond and inversely with the I⋅⋅⋅N halogen-bond length. The predictive power of this technique is validated on two previously unknown co-crystalline powders prepared mechanochemically. Single-crystal growth via co-sublimation and structure determination by single-crystal X-ray diffraction cross-validates the findings. Natural localized molecular-orbital analyses provide insight into the origins of the quadrupolar coupling constants.

Rapid Identification of Halogen Bonds in Co‐Crystalline Powders via 127I Nuclear Quadrupole Resonance Spectroscopy

Abstract127I nuclear quadrupole resonance (NQR) spectroscopy is established as a rapid and robust method to indicate the formation of iodine–nitrogen halogen bonds in co‐crystalline powders. Once the relevant spectral frequency range has been established, diagnostic 127I NQR spectra can be acquired in seconds. The method is demonstrated for a series of co‐crystals of 1,4‐diiodobenzene. Changes in the 127I quadrupolar coupling constant (CQ) by up to 74.4 MHz correlate with the length of the C−I donor covalent bond and inversely with the I⋅⋅⋅N halogen‐bond length. The predictive power of this technique is validated on two previously unknown co‐crystalline powders prepared mechanochemically. Single‐crystal growth via co‐sublimation and structure determination by single‐crystal X‐ray diffraction cross‐validates the findings. Natural localized molecular‐orbital analyses provide insight into the origins of the quadrupolar coupling constants.

Charge and nematic orders in AFe2As2(A=Rb,Cs) superconductors

We discuss the results of $^{75}$As Nuclear Quadrupole Resonance (NQR) and muon spin relaxation measurements in AFe$_2$As$_2$ (A= Cs, Rb) iron-based superconductors. We demonstrate that the crossover detected in the nuclear spin-lattice relaxation rate $1/T_1$ (around 150 K in RbFe$_2$As$_2$ and around 75 K in CsFe$_2$As$_2$), from a high temperature nearly localized to a low temperature delocalized behaviour, is associated with the onset of an inhomogeneous local charge distribution causing the broadening or even the splitting of the NQR spectra as well as an increase in the muon spin relaxation rate. We argue that this crossover, occurring at temperatures well above the phase transition to the nematic long-range order, is associated with a charge disproportionation at the Fe sites induced by competing Hund's and Coulomb couplings. In RbFe$_2$As$_2$ around 35 K, far below that crossover temperature, we observe a peak in the NQR $1/T_1$ which is possibly associated with the critical slowing down of electronic nematic fluctuations on approaching the transition to the nematic long-range order.

33S nuclear quadrupole resonance study of dibenzyl disulfide toward understanding of cross-linked structures in rubber

Experimental and theoretical investigations of a sulfur-33 electric-field-gradient (EFG) tensor of disulfide bonds in 33S-labled dibenzyl disulfide have been presented. Temperature dependence of quadrupolar frequencies, νQ, is observed in the temperature range between 80 and 280 K, in which single peaks appear in all the 33S nuclear quadrupole resonance (NQR) spectra. Analysis of nutation echo 33S NQR spectra at 200 K yields the quadrupolar coupling constant, CQ value, of 46.8(6) MHz and the asymmetry parameter, ηQ, of 0.48(7). The orientation of the 33S EFG tensor of the disulfide is obtained by quantum chemical calculations: the largest EFG tensor component, VZZ, is approximately perpendicular to the molecular plane (C-S-S), and the smallest component, VXX, is approximately 41° off the C-S bond. Extensive quantum chemical calculations are systematically performed to investigate dependences of 33S EFG tensors on changes of torsion angles in disulfide and trisulfide bonds, indicating that analysis of νQ and CQ values potentially makes it possible to assign the secondary structures of cross-linking in a rubber.

Enhancement of superconductivity by pressure-induced critical ferromagnetic fluctuations in UCoGe

A $^{59}$Co nuclear quadrupole resonance (NQR) was performed on a single-crystalline ferromagnetic (FM) superconductor UCoGe under pressure. The FM phase vanished at a critical pressure $P_c$, and the NQR spectrum just below $P_c$ showed phase separation of the FM and paramagnetic (PM) phases below Curie temperature $T_{\textrm{Curie}}$, suggesting first-order FM quantum phase transition (QPT). We found that the internal field was absent above $P_c$, but the superconductivity is almost unchanged. This result suggests the existence of the nonunitary to unitary transition of the superconductivity around $P_c$. Nuclear spin-lattice relaxation rate $1/T_1$ showed the FM critical fluctuations around $P_c$, which persist above $P_c$ and are clearly related to superconductivity in the PM phase. This FM QPT is understood to be a weak first order with critical fluctuations. $1/T_1$ sharply decreased in the superconducting (SC) state above $P_c$ with a single component, in contrast to the two-component $1/T_1$ in the FM SC state, indicating that the inhomogeneous SC state is a characteristic feature of the FM SC state in UCoGe.