Nuclear Quadrupole Resonance Study Research Articles

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.

Possible star-of-David pattern charge density wave with additional modulation in the kagome superconductor CsV3Sb5

AV3Sb5 (A = K, Rb, Cs) is a novel kagome superconductor coexisting with the charge density wave (CDW) order. Identifying the structure of the CDW order is crucial for understanding the exotic normal state and superconductivity in this system. Here, we report 51V nuclear magnetic resonance (NMR) and 121/123Sb nuclear quadrupole resonance (NQR) studies on kagome-metal CsV3Sb5. Below the CDW transition temperature TCDW ~ 98 K, an abrupt change of spectra was observed, indicating that the transition is of the first order. By further analyzing the spectra, we find that the CDW order is commensurate. And most remarkably, the obtained experimental results suggest that the charge modulation of the CDW order is of star-of-David pattern and accompanied by an additional charge modulation in bulk below T* ~ 40 K. Our results revealing the unconventional CDW order provide new insights into AV3Sb5.

Local Structure of Multinary Hybrid Lead Halide Perovskites Investigated by Nuclear Quadrupole Resonance Spectroscopy

Hybrid organic–inorganic lead halide perovskites have emerged as popular low-cost, solution-processable semiconductors owing to their outstanding optical and electronic characteristics. The structural characterization of these soft solids has proven challenging due to increased structural dynamics and static disorder. Nuclear quadrupole resonance (NQR) may serve as a powerful tool for probing the local structure of the halide anions in bulk and nanocrystalline forms of these perovskites. Here, we characterize the atomic structure of mixed-cation and mixed-anion solid solutions derived from cubic formamidinium lead iodide (FAPbI3), typically used in photovoltaics and photodetectors, using 127I NQR. Even minute quantities of Cs ions on FA sites or Br ions on I sites lead to a multitude of different local environments, readily seen by NQR spectroscopy. At 10% Cs, signatures of Cs-ion clustering arise, pointing to the onset of the phase separation, observed by diffraction methods at higher Cs contents. On the contrary, Br-ion distribution appears homogeneous across all Br-to-I ratios. We anticipate that halide NQR studies will be indispensable for understanding the atomistic structure of diverse multinary metal halides, also in their diverse forms—from single crystals to thin films and nanocrystals.

A Low-Cost Digital Pulsed Coherent Spectrometer for Investigation of NQR in Layered Semiconductor GaSe and InSe Crystals

A low-cost digital pulsed nuclear quadrupole resonance (NQR) radio-spectrometer is proposed, all main modules of digital processing and synthesis of which on the field-programmable gate array (FPGA) are implemented. The input sensitivity of the device is of the order of 3 μV to 5 μV which allows conducting NQR studies in samples of relatively small dimensions. The application of the developed methods of NQR pulsed radio spectroscopy made it possible to increase spectral resolution, improve spectral shape and significantly reduce the time of research. In the case of studying InSe and GaSe crystals, spectra with signal-to-noise ratio (SNR) values of 41.9 dB were observed in samples with a volume of 0.1 cm3. As the results of the research have shown, the characteristics of the proposed spectrometer make it effective when used to observe free induction decay (FID) signals of a significant number of isotopes of elements with quadrupolar nuclei.

Nuclear Quadrupole Resonance (NQR)—A Useful Spectroscopic Tool in Pharmacy for the Study of Polymorphism

Nuclear Quadrupole Resonance (NQR) spectroscopy has been known for 70 years. It is suitable for the study of measured (poly)crystalline chemical compounds containing quadrupole nuclei (nuclei with spin I ≥ 1) where the characteristic NQR frequencies represent the fingerprints of these compounds. In several cases, 14N NQR can distinguish between the polymorphic crystalline phases of active pharmaceutical ingredients (APIs). In order to further stimulate 14N NQR studies, we review here several results of API polymorphism studies obtained in Ljubljana laboratories: (a) In sulfanilamide, a clear distinction between three known polymorphs (α, β, γ) was demonstrated. (b) In famotidine, the full spectra of all seven different nitrogen positions were measured; two polymorphs were distinguished. (c) In piroxicam, the 14N NQR data helped in confirming the new polymorphic form V. (d) The compaction pressure in the tablet production of paracetamol, which is connected with linewidth change, can be used to distinguish between producers of paracetamol. We established that paracetamol in the tablets of six different manufacturers can be identified by 14N NQR linewidth. (e) Finally, in order to get an extremely sensitive 14N NQR spectrometer, the optical detection of the 14N NQR signal is mentioned.

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.

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.

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.

Structural phase transition, antiferromagnetism and two superconducting domes in LaFeAsO1-xFx (0 < x ≤ 0.75)

We report $^{75}$As nuclear magnetic resonance (NMR) / nuclear quadrupole resonance (NQR) and transmission electron microscopy (TEM) studies on LaFeAsO$_{1-x}$F$_{x}$. There are two superconducting domes in this material. The first one appears at 0.03 $\leq$ $x$ $\leq$ 0.2 with $T_{\rm c}$$^{max}$ = 27 K, and the second one at 0.25 $\leq$ $x$ $\leq$ 0.75 with $T_{\rm c}$$^{max}$ = 30 K. By NMR and TEM, we demonstrate that a $C4$-to-$C2$ structural phase transition (SPT) takes place above both domes, with the transition temperature $T_{\rm s}$ varying strongly with $x$. In the first dome, the SPT is followed by an antiferromagnetic (AF) transition, but neither AF order nor low-energy spin fluctuations are found in the second dome. In LaFeAsO$_{0.97}$F$_{0.03}$, we find that AF order and superconductivity coexist microscopically via $^{75}$As nuclear spin-lattice relaxation rate (1/$T_1$) measurements. In the coexisting region, 1/$T_1$ decreases at $T_{\rm c}$ but becomes to be proportional to $T$ below 0.6$T_{\rm c}$, indicating gapless excitations. Therefore, in contrast to the early reports, the obtained phase diagram for $x \leq$ 0.2 is quite similar to the doped BaFe$_{2}$As$_{2}$ system. The electrical resistivity in the second dome can be fitted by $\rho = {{\rho }_{0}}+A{{T}^{n}}$ with $n$ = 1 and a maximal coefficient $A$ at around $x_{opt}$ = 0.5$\sim$0.55 where $T_{\rm s}$ extrapolates to zero and $T_{\rm c}$ is the maximal, which suggest the importance of quantum critical fluctuations associated with the SPT. We have constructed a complete phase diagram of LaFeAsO$_{1-x}$F$_{x}$, which provides insight into the relationship between SPT, antiferromagnetism and superconductivity.

Microscopic evidence for magnetic ordering in [formula omitted]: 63,65Cu nuclear quadrupole resonance study

We have conducted 63,65Cu nuclear quadrupole resonance (NQR) measurements on A-site ordered perovskite compounds LaCu3Ru4O12 and NdCu3Ru4O12 to investigate their ground state and spin fluctuations. While there is only one Cu site in the crystal structure, multiple NQR resonance lines were observed. This is presumed to be due to the presence of slight distortion and lattice defects in the samples. The nuclear spin-lattice relaxation rate divided by temperature, 1/T1T, for LaCu3Ru4O12 showed almost constant value indicating the Fermi-liquid state. A remarkable increase in 1/T1T due to spin fluctuations was observed in NdCu3Ru4O12. Furthermore, an evident magnetic phase transition at TM=0.6K was revealed from the distinct peak of 1/T1T and the broadening of the NQR spectrum.

Sb-NMR/NQR studies of heavy fermion system YbRhSb

We report a study of 121Sb nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) in a Yb-based heavy fermion system YbRhSb using a single crystal. Sharp 121Sb-NMR lines were observed for each crystal axis for B‖a,b,c. From comparison with observed Sb-NMR spectra and numerical simulations, electric field gradient (EFG) parameters and Knight shift parameters are obtained at 10 K. The obtained quadrupole frequency, asymmetry parameter, isotropic Knight shift and anisotropic principal values of Knight shift tensors are νQ = 18.8 MHz, , and , respectively. We also succeeded in observing 121Sb-NQR signals at around 19.5 and 37 MHz, which are reproduced by the nuclear quadrupole Hamiltonian with νQ = 18.8 MHz and η = 0.2. We mention the relation between the anisotropy of the Knight shift and magnetic susceptibility. Our NMR/NQR results suggest that the weak ferromagnetism in YbRhSb is ascribed to a canted antiferromagnetic state.

Charge fluctuations and nodeless superconductivity in quasi-one-dimensionalTa4Pd3Te16revealed byTe125-NMR andTa181-NQR

We report $^{125}$Te nuclear magnetic resonance and $^{181}$Ta nuclear quadrupole resonance studies on single-crystal Ta$_{4}$Pd$_{3}$Te$_{16}$, which has a quasi-one-dimensional structure and superconducts below $T_{\rm c}=4.3$ K. $^{181}$Ta with spin $I=7/2$ is sensitive to quadrupole interactions, while $^{125}$Te with spin $I=1/2$ can only relax by magnetic interactions. By comparing the spin-lattice relaxation rate ( $1/T_{1}$) of $^{181}$Ta and $^{125}$Te, we found that electric-field-gradient (EFG) fluctuations develop below $80$ K. The EFG fluctuations are enhanced with decreasing temperature due to the fluctuations of a charge density wave that sets in at $T_{\rm CDW}=20$ K, below which the spectra are broadened and $1/T_{1}T$ drops sharply. In the superconducting state, $1/T_{1}$ shows a Hebel-Slichter coherence peak just below $T_{\rm c}$ for $^{125}$Te, indicating that Ta$_{4}$Pd$_{3}$Te$_{16}$ is a full-gap superconductor without nodes in the gap function. The coherence peak is absent in the $1/T_{1}$ of $^{181}$Ta due to the strong EFG fluctuations.

Extended nuclear quadrupole resonance study of the heavy-fermion superconductorPuCoGa5

PuCoGa$_5$ has emerged as a prototypical heavy-fermion superconductor, with its transition temperature ($T_c\simeq18.5$ K) being the highest amongst such materials. Nonetheless, a clear description as to what drives the superconducting pairing is still lacking, rendered complicated by the notoriously intricate nature of plutonium's 5$f$ valence electrons. Here, we present a detailed $^{69,71}$Ga nuclear quadrupole resonance (NQR) study of PuCoGa$_5$, concentrating on the system's normal state properties near to $T_c$ and aiming to detect distinct signatures of possible pairing mechanisms. In particular, the quadrupole frequency and spin-lattice relaxation rate were measured for the two crystallographically inequivalent Ga sites and for both Ga isotopes, in the temperature range 1.6 K - 300 K. No evidence of significant charge fluctuations is found from the NQR observables. On the contrary, the low-energy dynamics is dominated by anisotropic spin fluctuations with strong, nearly critical, in-plane character, which are effectively identical to the case of the sister compound PuCoIn$_5$. These findings are discussed within the context of different theoretical proposals for the unconventional pairing mechanism in heavy-fermion superconductors.

Nuclear Quadrupole Resonance Study of Proton and Deuteron Migration in Short Strong Hydrogen Bonds Formed in Molecular Complex 3,5-Dinitrobenzoic Acid–Nicotinic Acid and in Deuterated 3,5-Pyridinedicarboxylic Acid

Temperature dependences of the 14N nuclear quadrupole resonance (NQR) frequencies have been measured in molecular complex 3,5-dinitrobenzoic acid–nicotinic acid (35DBNA) and in deuterated 3,5-pyridinedicarboxylic acid (DPDA). In deuterated DPDA, the temperature dependences of the deuterium quadrupole coupling constants and asymmetry parameters η have also been measured. In 35DBNA, the magnitude of the quadrupole coupling constant of the pyridine nitrogen agrees with the experimentally observed proton transfer. No proton exchange (O–H···N ↔ O–···H–N+) is observed. The temperature dependence of the 14N quadrupole coupling constant is analyzed in a model of a resonance hybrid of two extreme electron configurations of the molecules. The energy difference of the two extreme electron configurations is determined. In the same model, we analyzed previously published 14N NQR data of the NHO hydrogen bond in nondeuterated 3,5-pyridinedicarboxylic acid. The 14N NQR data in DPDA show the presence of a quasi-continuou...

121,123Sb and 75As NMR and NQR investigation of the tetrahedrite (Cu12Sb4S13) – Tennantite (Cu12As4S13) system and other metal arsenides

This work is motivated by the recent developments in online minerals analysis in the mining and minerals processing industry via nuclear quadrupole resonance (NQR). Here we describe a nuclear magnetic resonance (NMR) and NQR study of the minerals tennantite (Cu12As4S13) and tetrahedrite (Cu12 Sb4S13). In the first part NQR lines associated with 75As in tennantite and 121,123Sb isotopes in tetrahedrite are reported. The spectroscopy has been restricted to an ambient temperature studies in accord with typical industrial conditions. The second part of this contribution reports nuclear quadrupole-perturbed NMR findings on further, only partially characterised, metal arsenides. The findings enhance the detection capabilities of NQR based analysers for online measurement applications and may aid to control arsenic and antimony concentrations in metal processing stages.

Ferromagnetic Spin Fluctuation and Unconventional Superconductivity in Rb2Cr3As3 Revealed by 75As NMR and NQR.

We report (75)As nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) studies on the superconductor Rb(2)Cr(3)As(3) with a quasi-one-dimensional crystal structure. Below T∼100 K, the spin-lattice relaxation rate (1/T(1)) divided by temperature, 1/T(1)T, increases upon cooling down to T(c)=4.8 K, showing a Curie-Weiss-like temperature dependence. The Knight shift also increases with decreasing temperature. These results suggest ferromagnetic spin fluctuation. In the superconducting state, 1/T(1) decreases rapidly below T(c) without a Hebel-Slichter peak, and follows a T(5) variation below T∼3 K, which points to unconventional superconductivity with point nodes in the gap function.

Zero-field NMR and NQR studies of magnetically ordered state in charge-ordered EuPtP

EuPtP undergoes two valence transitions and has two kinds of valence states of Eu ions at low temperatures. In the charge-ordered state, this compound shows an antiferromagnetic order ascribed to magnetic divalent Eu ions. We investigated the antiferromagnetically ordered state of EuPtP by nuclear magnetic resonance (NMR) measurement and nuclear quadrupole resonance (NQR) measurement in a zero external magnetic field. The observed $^{153}\mathrm{Eu}$ NMR signals of a magnetic divalent state and $^{151,153}\mathrm{Eu}$ NQR signals of a nonmagnetic trivalent state clearly demonstrate that the spins order in the hexagonal basal plane and the internal magnetic field is not canceled out, even at the ${\mathrm{Eu}}^{3+}$ layers which are in the middle of magnetic ${\mathrm{Eu}}^{2+}$ layers. In addition, the observation of ${}^{31}\mathrm{P}$ and $^{195}\mathrm{Pt}$ NMR spectra allowed us to discuss a possible magnetic structure. We also evaluated the nuclear quadrupole frequencies for both ${\mathrm{Eu}}^{2+}$ and ${\mathrm{Eu}}^{3+}$ ion states.

Application of 57Fe Mössbauer spectroscopy as a tool for mining exploration of bornite (Cu5FeS4) copper ore

Nuclear resonance methods, including Mossbauer spectroscopy,are considered as unique techniques suitable for remote on-line mineralogical analysis. The employment of these methods provides potentially significant commercial benefits for mining industry. As applied to copper sulfide ores, Mossbauer spectroscopy method is suitable for the analysis noted. Bornite (formally Cu5FeS4) is a significant part of copper ore and identification of its properties is important for economic exploitation of commercial copper ore deposits. A series of natural bornite samples was studied by 57Fe Mossbauer spectroscopy. Two aspects were considered: reexamination of 57Fe Mossbauer properties of natural bornite samples and their stability irrespective of origin and potential use of miniaturized Mossbauer spectrometers MIMOS II for in-situ bornite identification. The results obtained show a number of potential benefits of introducing the available portative Mossbauer equipment into the mining industry for express mineralogical analysis. In addition, results of some preliminary 63,65Cu nuclear quadrupole resonance (NQR) studies of bornite are reported and their merits with Mossbauer techniques for bornite detection discussed.

Nuclear Quadrupole Resonance Study of Hydrogen Bonds in Solid 2-Methylbenzimidazole and 5,6-Dimethylbenzimidazole

Substituted imidazole and benzimidazole often form polar hydrogen-bonded chains in the solid state. 2-Methylbenzimidazole is known to be a high-temperature organic ferroelectric. We have measured t...

Sb NQR study of the filled skutterudite CeFe4Sb12 synthesized under high pressure

We report the results of Sb nuclear quadrupole resonance (NQR) measurements on the filled skutterudite CeFe4Sb12 synthesized under high pressure (HP) and compare them with those for the sample synthesized under ambient pressure (AP) to understand the influence of the Ce-site filling fraction. The NQR spectra for the HP sample are much sharper than those for the AP sample, suggesting that the Ce filling fraction is higher. Also, the nuclear spin-lattice relaxation rate 1/T 1 follows an exponential decrease 1/T 1 ∝ exp(−Δ/k B T), with the gap being Δ/k B = 270 K at temperatures above 100 K, which is larger than that for the AP sample. This result suggests that the c-f hybridization is enhanced by increasing the Ce-site filling fraction.