Nuclear Quadrupole Resonance Line Research Articles

Experimental nuclear quadrupole resonance and computational study of the structurally refined topological semimetal TaSb2

The local electric field gradients and magnetic dynamics of TaSb2 have been studied using Sb121, Sb123, and Ta181 nuclear quadrupole resonance (NQR) with density functional theory (DFT) calculations using XRD-determined crystal structures. By measuring all structurally expected 13 NQR lines, the nuclear quadrupole coupling constant (νQ) and asymmetric parameter (η) for Ta, Sb(1), and Sb(2) sites were obtained. These values are all in good agreement with the presented DFT calculations. Principal axes of the electric field gradients was determined for a single-crystal sample by measuring the angular dependencies of NMR frequency under a weak magnetic field. The unusual temperature dependence of η(T) of Sb(2) hints at the suppressed thermal expansion along the a axis. Spin-lattice relaxation rate (1/T1T) measurements reveal an activated-type behavior and an upturn below 30 K. Neither the low-temperature upturn nor the high-temperature activation-type behaviors are reproduced by the calculated 1/T1T based on the calculated density of states (DOS). On the other hand, the agreement between the calculated DOS and specific heat measurements indicates that the band renormalization is small. This fact indicates that TaSb2 deviates from the simple semimetal scenario, and magnetic excitations are not captured by Fermi liquid theory. Published by the American Physical Society 2024

Pseudo-gap in RuGa3: A microscopic point of view

We report a detailed study of the nature of the RuGa3in-gap states by means of precision microscopic methods: nuclear quadrupole resonance (NQR), nuclear magnetic resonance (NMR), and pump-probe spectroscopy. We observe a pronounced splitting of 69Ga nuclear spin-lattice relaxation curves below ∼40 K and between 70 and 145 K, although the corresponding NQR lines remain narrow over the entire temperature range under study. The slow relaxing component behaves like a typical phonon-induced relaxation way, while the fast relaxing one demonstrates signatures of paramagnetic (below ∼40 K) and activation (between 70 and 145 K) mechanisms. Moreover, additional Ga’ and Ga’’ positions with anomalously low electric field gradient were revealed for the first time for IrIn3-type structure gallides, which stay almost unchanged, at least up to 77 K. The observed microscopic features are accompanied with in-gap states saturation or depleting, which is seen as the resistivity mechanism crossover at ∼180 K and electron localization below 145 K evidenced by pump-probe spectroscopy. Based on our experimental results, we associate this pseudo-gap like behavior with inhomogeneously distributed electronic density defects, which manifest at both micro- (nuclear spin and phonon dynamics) and macroscale (bulk transport properties such as resistivity).

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.

Freezing of the Lattice in the Kagome Lattice Heisenberg Antiferromagnet Zn-Barlowite ZnCu_{3}(OD)_{6}FBr.

We use ^{79}Br nuclear quadrupole resonance (NQR) to demonstrate that ultraslow lattice dynamics set in below the temperature scale set by the Cu-Cu superexchange interaction J (≃160 K) in the kagome lattice Heisenberg antiferromagnet Zn-barlowite. The lattice completely freezes below 50K, and ^{79}Br NQR line shapes become twice broader due to increased lattice distortions. Moreover, the frozen lattice exhibits an oscillatory component in the transverse spin echo decay, a typical signature of pairing of nuclear spins by indirect nuclear spin-spin interaction. This indicates that some Br sites form structural dimers via a pair of kagome Cu sites prior to the gradual emergence of spin singlets below ∼30 K. Our findings underscore the significant roles played by subtle structural distortions in determining the nature of the disordered magnetic ground state of the kagome lattice.

Barnett field, rotational Doppler effect, and Berry phase studied by nuclear quadrupole resonance with rotation

We report the observation of the Barnett field, rotational Doppler effect, and Berry phase using the rotating nuclear quadrupole resonance (NQR) method. We have developed coil-spinning techniques that enable us to systematically study the effects of rotation in setups involving rotation of the signal detector, rotation of the sample, and simultaneous rotation of both the signal detector and sample. Applying these setups to NQR measurements, we observe NQR line splittings in which the spectral structures are clearly distinct among the setups. By analyzing these structures, we clarify the origin of the NQR line splittings and discuss the relationship between the rotational Doppler effect, Barnett field effect, and Berry phase in terms of the rotational degrees of freedom, such as the relative rotation and the sample rotation itself, and the observation frame of reference. We also provide clear evidence of the difference between the rotational Doppler effect and the Barnett field and the equivalence of the Barnett field and the Berry phase.

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.

Motional freedom of dimethylammonium ions in a cyanoelpasolite, [(CH3)2NH2]2KCo(CN)6, which exhibits phase transition associated with a distinct change in dielectric property.

The temperature dependence of the 1H nuclear magnetic resonance spin-lattice relaxation time T1 of [(CH3)2NH2]2KCo(CN)6 and the partially deuterated analogue [(CD3)2NH2]2KCo(CN)6 has been reported. A change in the molecular motion of organic cations through the first-order phase transition at Tc = 246 K has been discussed. Although this first-order transition has been reported as an isosymmetric transition, in which the space group of the crystal does not change, the number of the 14N nuclear quadrupole resonance line changed from three in the high-temperature phase to twelve in the low-temperature phase indicating the lowering of crystal symmetry.

NQR, NMR, and X-ray crystal structure studies of [4-C2H5-C6H4NH3]2MBr4 (M=Zn, Cd)

Abstract The crystal structure of [4-C2H5-C6H4NH3]2ZnBr4 (1) has been determined at 150(2) K: triclinic, P1̅, a=724.82(2), b=1194.20(4), c=1322.26(4) pm, α=74.151(3), β=80.887(3), γ=80.434(3)°, and Z=2. There are two crystallographically independent cations in the unit cell of 1: one has its benzene ring perpendicular to the crystallographic a axis of the unit cell and the other one has its benzene ring perpendicular to the c axis. These cations are alternatingly located along the c axis and form organic layers, and the ZnBr4 anions form inorganic layers in between. Zn–Br···H–N hydrogen bonds are formed between cations and anions. In accordance with the crystal structure, four nuclear quadrupole resonance (NQR) lines of 81Br were observed. The temperature dependence of the 81Br NQR frequencies between 77 and 320 K shows a peculiar feature which is not due to a structural phase transition. The measurement of 13C nuclear magnetic resonance spectra at around T=340 K indicates a redistribution of cations. The temperature dependence of 81Br NQR frequencies and differential thermal analysis measurements show that [4-C2H5-C6H4NH3]2CdBr4 (2) undergoes a structural phase transition at around 190 K.

Sb121,123nuclear quadrupole resonance as a microscopic probe in the Te-doped correlated semimetalFeSb2: Emergence of electronic Griffith phase, magnetism, and metallic behavior

$^{121,123}Sb$ nuclear quadrupole resonance (NQR) was applied to $Fe(Sb_{1-x}Te_x)_2$ in the low doping regime (\emph{x = 0, 0.01} and \emph{0.05}) as a microscopic zero field probe to study the evolution of \emph{3d} magnetism and the emergence of metallic behavior. Whereas the NQR spectra itself reflects the degree of local disorder via the width of the individual NQR lines, the spin lattice relaxation rate (SLRR) $1/T_1(T)$ probes the fluctuations at the $Sb$ - site. The fluctuations originate either from conduction electrons or from magnetic moments. In contrast to the semi metal $FeSb_2$ with a clear signature of the charge and spin gap formation in $1/T_1(T)T ( \sim exp/ (\Delta k_BT) ) $, the 1\% $Te$ doped system exhibits almost metallic conductivity and a almost filled gap. A weak divergence of the SLRR coefficient $1/T_1(T)T \sim T^{-n} \sim T^{-0.2}$ points towards the presence of electronic correlations towards low temperatures wheras the \textit{5\%} $Te$ doped sample exhibits a much larger divergence in the SLRR coefficient showing $1/T_1(T)T \sim T^{-0.72} $. According to the specific heat divergence a power law with $n\ =\ 2\ m\ =\ 0.56$ is expected for the SLRR. Furthermore $Te$-doped $FeSb_2$ as a disordered paramagnetic metal might be a platform for the electronic Griffith phase scenario. NQR evidences a substantial asymmetric broadening of the $^{121,123}Sb$ NQR spectrum for the \emph{5\%} sample. This has purely electronic origin in agreement with the electronic Griffith phase and stems probably from an enhanced $Sb$-$Te$ bond polarization and electronic density shift towards the $Te$ atom inside $Sb$-$Te$ dumbbell.

Model - free approach to quadrupole spin relaxation in solid 209Bi-aryl compounds.

Nuclear Quadrupole Resonance (NQR) experiments were performed for deuterated and non-deuterated triphenylbismuth (BiPh3) to inquire into 209Bi relaxation mechanisms. The studies are motivated by the idea of exploiting Quadrupole Relaxation Enhancement (QRE) as a novel contrast mechanism for Magnetic Resonance Imaging. From this perspective relaxation features of nuclei possessing quadrupole moment (quadrupole nuclei) are of primary importance for the contrast effect. Spin-spin relaxation rates associated with the NQR lines were described in terms of the Redfield relaxation theory assuming that the relaxation is caused by fluctuations of the electric field gradient tensor at the position of the quadrupole nucleus that are described by an exponential correlation function. The description referred to as a model-free approach is an analogy of the description used for paramagnetic contrast agents. It was demonstrated that for the deuterated compound this approach captures the essential features of 209Bi relaxation, but it should not be applied for non-deuterated compounds as dipolar interactions between neighbouring protons and the quadrupole nucleus considerably contribute to the relaxation of the last one. Thus, the relaxation scenario for species containing quadrupole nuclei is fundamentally different than for paramagnetic contrast agents and this fact has to be taken into account when predicting contrast effects based on QRE.

X-ray and NQR studies of bromoindate(III) complexes: [C2H5NH3]4InBr7, [C(NH2)3]3InBr6, and [H3NCH2C(CH3)2CH2NH3]InBr5

Abstract The crystal structures of [C2H5NH3]4InBr7(1), [C(NH2)3]3InBr6(2), and [H3NCH2C(CH3)2CH2NH3]InBr5(3) were determined at 100(2) K: monoclinic, P21 /n, a=1061.94(3), b=1186.40(4), c=2007.88(7) pm, β= 104.575(1)°, Z=4 for 1; monoclinic, C2/c, a=3128.81(12), b=878.42(3), c=2816.50(10) pm, β=92.1320(10)°, Z=16 for 2; orthorhombic, P212121, a=1250.33(5), b=1391.46(6), c=2503.22(9) pm, Z=4 for 3. The structure of 1 contains an isolated octahedral [InBr6]3− ion and a Br− ion. The structure of 2 contains three different isolated octahedral [InBr6]3− ions. The structure of 3 has a corner-shared double-octahedral [In2Br11]5− ion and an isolated tetrahedral [InBr4]− ion. The 81Br nuclear quadrupole resonance (NQR) lines of the terminal Br atoms of the compounds are widely spread in frequency, and some of them show unusual positive temperature dependence. These observations manifest the N−H···Br−In hydrogen bond networks developed between the cations and anions to stabilize the crystal structures. The 81Br NQR and differential thermal analysis (DTA) measurements have revealed the occurrence of unique phase transitions in 1 and 3. When the bond angles were estimated from the electric field gradient (EFG) directions calculated by the molecular orbital (MO) methods, accurate values were obtained for [InBr6]3− of 1 and for [In2Br11]5− and [InBr4]− of 3, except for several exceptions in those for the latter two ions. On the other hand, the calculations of 81Br NQR frequencies have produced up to 1.4 times higher values than the observed ones.

Physical properties optimization of polycrystalline LiFeAs

We present a study of parameter optimization for synthesizing truly stoichiometric polycrystalline LiFeAs. Stoichiometric LiFeAs has been prepared in a very broad range of synthesis temperature (200–900°C) under otherwise exactly the same conditions, and has been characterized by structural, magnetic, transport, nuclear quadrupole resonance (NQR), and specific heat measurements. Our study showed that the LiFeAs phase is formed at 200°C with a large amount of impurity phases. The amount of these impurity phases reduces with increasing synthesis temperature and the clean LiFeAs phase is obtained at a synthesis temperature of 600°C. Magnetic susceptibility and resistivity measurements confirmed that the superconducting properties such as the critical temperature Tc, and the upper critical field Hc2 do not depend on the synthesis temperature (≤700°C), remaining at almost the same value of ∼19K and ∼40T, respectively. However, the width ΔTc of the transition and the NQR line width decrease with increasing the synthesis temperature and reached to minimum value for the synthesis temperature of 600°C. Our careful analysis suggests that the best sample obtained at 600°C is optimal concerning the low resistivity, high residual resistivity ratio (RRR), low ΔTc, high Tc and Hc2, and a small NQR line width with values which are comparable to that reported for LiFeAs single crystals. Specific heat measurements confirmed the bulk superconducting nature of the samples. The Hc2 value estimated from the specific heat is consistent with that of the resistivity measurements. Concisely, 600°C synthesis temperature yields optimal high quality polycrystalline LiFeAs bulk samples. Further improvement of the quality of the sample prepared at 600°C could be obtained by a controlled slow cooling process. Microstructural analysis reveals that the abundance of micro-cracks becomes strongly reduced by the slow cooling process, resulting in an increase in clean and well-connected grain boundaries.

NQR and X-ray crystal structure studies of cadmium halide complexes: [C(NH2)3]CdI3 and [4-ClC6H5NH3]3CdBr5

Abstract The crystal structures of [C(NH2)3]CdI3 (1) and [4-ClC6H5NH3]3CdBr5 (2) have been determined at 100 K: monoclinic, Cc, a = 828.75(3) pm, b = 1615.31(5) pm, c = 810.64(3) pm, and β = 106.5820(10)° for 1; monoclinic, P21 /c, a = 1486.93(5) pm, b = 794.31(3) pm, c = 2290.59(7) pm, and β = 99.6830(10)° for 2. The structure of 1 has an infinite chain of anions consisting of [CdI4] tetrahedra sharing two corners. The structure of 2 has an infinite chain of anions consisting of [CdBr6] octahedra sharing two corners in cis positions. In both structures, isolated cations are connected to the anion chains through weak hydrogen bonds Cd–X···H to result in three-dimensional network structures. In accordance with the crystal structures, three 127I (m = ±1/2 ↔ m = ±3/2), five 81Br, and three 35Cl nuclear quadrupole resonance (NQR) lines were observed for 1 and 2. The NQR spectra reflect the anion chain structures and their weak hydrogen bonds. The MO calculations of the models [Cd5I16]6– for 1 and [Cd3Br16]10– for 2 estimate only about half the values for the NQR frequencies but give accurate electric field gradient directions.

Analysis of 27Al- and 93Nb-NMR spectra of PrNb2Al20 single crystal

We report the results of 27Al- and 93Nb- nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements in PrNb2Al20 single crystals. The field angle dependence of the observed 93Nb-NMR lines for the single crystal at around 5 T and at 50 K is reproduced by a simulation using previously reported NQR parameters νQ,Nb ≈ 1.82 MHz and ηNb ≈ 0, while 27Al-NMR lines were not reproduce by the previously reported NQR parameters νQ,Al(3) ≈ 1.53 MHz and ηAl(3) ≈ 0.17. By reexamining and reconsidering the NMR and NQR lines for powder samples, we obtained a correct NQR parameters for Al(3) site to be νQ,Al(3),new ≈ 1 MHz and ηAl(3),new ≈ 0.4.

Electron spin echo envelope modulation of molecular motions of deuterium nuclei

Electron Spin Echo Envelope Modulation (ESEEM) spectroscopy is a powerful technique for the study of hyperfine interactions between an unpaired electron and nearby nuclei in solids, and is employed in quantitative structural studies. Here, we describe the use of ESEEM to study the slow motion of deuterium nuclei using their nuclear quadrupole resonance (NQR) line shapes. Two ESEEM techniques were employed: the conventional three-pulse ESEEM experiment, π/2 – τ – π/2 – T– π/2 – τ – echo, and the four-pulse ESEEM, π/2 – τ – π/2 – T/2 – π – T/2 – π/2 – τ – echo, with the time variable T scanned in both cases. The nitroxide free radical 4-tert-butyliminomethyl-2,2,5,5-tetramethyl(d12)-3-imidazoline-1-oxyl with four deuterated methyl groups was investigated in a glassy ortho-terphenyl matrix over a wide temperature range. It was shown that four-pulse ESEEM allowed measurement of the nearly pure 2H NQR line shape. Between 90K and 120K, the ESEEM spectra change drastically. At low temperatures, four-pulse ESEEM spectra show a Pake-like pattern, which evolves into a single line at higher temperatures, which is typical for NQR of rotating methyl CD3 groups. Comparison with literature data on NQR allows estimation of the reorientation rate, k. At ∼100K, where the spectral changes are most pronounced, k was found to be ∼105s−1. The spectral linewidths for the three-pulse ESEEM were found to decrease similarly with increasing temperature; so the three-pulse technique is also capable to detect motion of this type. The ESEEM approach, along with site-directed spin labeling, may be useful for detection of motional transitions near the spin labels in biological systems, when information on motion is required in a wide temperature range.

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.

Two-Frequency Nuclear Quadrupole Resonance for Line Identification

Two possible modifications of two-frequency 14N nuclear quadrupole resonance (NQR) technique for the identification of resonance lines in NQR spectra have been studied and compared. The first one is the use of a single coil for two close frequencies (in our case, ν + and ν − lines), while the second one utilizes two coils for two different resonance frequencies. Both two-frequency methods have been applied to the carbamazepine which is a substance with a low asymmetry parameter η of the electric field gradient tensor in crystal. It has been shown that both approaches can be applied for the identification of the 14N NQR lines.

Weak itinerant antiferromagnetism in PuIn3 explored using 115In nuclear quadrupole resonance

The results of 115In nuclear quadrupole resonance (NQR) measurements on PuIn3 are reported. Three of the four NQR lines of 115In expected for nuclear spin I = 9/2 are observed. The equal spacing of these lines at 20 K yields the NQR frequency of νQ = 10.45 MHz, and the asymmetry parameter of the electric field gradient η = 0. The NQR line profile and the nuclear spin–lattice relaxation rate 1/T1 display an abrupt change at 14 K, which is associated with the onset of long-range antiferromagnetic order. The temperature dependences of the staggered magnetization MQ(T), extracted from the NQR spectra, and 1/T1 below TN = 14 K are well explained by the self-consistent renormalization (SCR) theory for spin fluctuations. In addition, the scaling between T1T and MQ(T)/MQ(0) is also consistent with the predictions of SCR theory, providing further evidence that PuIn3 is a weak itinerant antiferromagnet in which spin fluctuations around the antiferromagnetic wavevector play a major role in the system’s behavior at finite temperatures.

Zeeman shift – A tool for assignment of 14N NQR lines of nonequivalent 14N atoms in powder samples

The use of Zeeman perturbed 14N nuclear quadrupole resonance (NQR) to determine the ν + and ν − 14N lines in polycrystalline samples with several nonequivalent nitrogen atoms was investigated. The 14N NQR line shift due to a weak external Zeeman magnetic field was calculated, assuming isotropic distribution of EFG tensor directions. We calculated the broad line distribution of the ν + and ν − line shifts and experimentally confirmed the calculated Zeeman field dependence of singularities (NQR peaks) in cyclotrimethylenetrinitramine (RDX) and aminotetrazole monohydrate (ATMH). The calculated and measured frequency shifts agreed well. The proposed measurement method enabled determination of which 14N NQR lines in ATMH belong to ν + and which to ν − transitions.

Measurement of dipolar structure of 17O nuclear quadrupole resonance lines by three-frequency irradiation

A modification of nuclear quadrupole double resonance with coupled multiplet is proposed which can be used for the measurement of the dipolar structure of the 17O nuclear quadrupole resonance lines in case of a strong 1H17O dipolar interaction. The technique is based on magnetic field cycling between a high magnetic field and zero magnetic field and on the simultaneous application of three rf magnetic fields with the frequencies that are close to the three 17O NQR frequencies ν5/2−1/2>ν5/2−3/2⩾ν3/2−1/2 during the time spent in zero static magnetic field. When the sum of the two lower irradiation frequencies ν1+ν2 is not equal to the highest irradiation frequency ν, the three-frequency irradiation increases the proton relaxation rate in zero magnetic field and consequently decreases the proton NMR signal at the end of the magnetic field cycle. The new technique is theoretically analyzed and compared to the single-frequency and two-frequency irradiation techniques. It is shown that the sensitivity of the new technique exceeds the sensitivity of the two-frequency irradiation technique. As a test of the new technique we measured the shape of the highest-frequency 17O NQR line in paraelectric KH2PO4.