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.     

Spins,moments and charge radii in the isotopic series181Hg-191Hg

The hyperfine structure splitting and the isotope shift in the (6 s^{2 1}S₀ - 6s 6p³P₁,λ=2,537 Å) line of very neutron deficient Hg isotopes were determined by the β radiation detected optical pumping method (β-RADOP). In addition, nuclear magnetic resonance was observed in the atomic ground state. The results are Mean-square nuclear charge radii are calculated. Interpreting the sudden change of nuclear radius between¹⁸⁷Hg and¹⁸⁵Hg δ〈r²〉^187,185=0.42(5)fm² as oblate-prolate shape transition, one obtains δ〈β²〉 =0.054(5).     

Electron spin resonance studies of 199HgH, 201HgH, 199HgD and 201HgD isolated in neon and argon matrices at 4K: an electronic structure investigation

Various isotopomers of the mercury hydride radical (HgH) have been generated in a microwave discharge and trapped in neon and argon matrices at 4 K for electron spin resonance (ESR) investigations. Both the dipolar (A_dip) and isotropic (A_iso) components of the nuclear hyperfine interactions have been directly measured for ¹⁹⁹Hg, ²⁰¹Hg, H and D. Electronic structure information for HgH in its X²Σ ground state obtained from the hyperfine data is compared with theoretical results from several different computational methods. The hyperfine interactions in HgH are unusually large with A_iso(¹⁹⁹Hg) = 6859(3), A_dip(¹⁹⁹Hg) = 446(3), A_iso(H) = 730(2) and A_dip(H) = 0(2) MHz. A standard analysis of the hyperfine interactions demonstrates the need for a more in-depth theoretical treatment of HgH that should include relativistic effects. An interesting shift in spin density is observed when deuterium replaces hydrogen in HgH. The decreased spin density on deuterium, which was demonstrated in earlier studies, can now be more fully investigated since these new measurements confirm an associated increase in spin density on mercury     

75As, 63Cu NMR and NQR characterization of selected arsenic minerals

The direct measurement and identification of solid state arsenic phases using ⁷⁵As NMR is made difficult by the simultaneous conditions of large quadrupole moment and low coordination symmetry in many compounds. However, specific arsenic minerals can efficiently be detected and discriminated via nuclear quadrupolar resonance (NQR). We report on the first NMR and NQR measurements in the natural minerals enargite (Cu₃AsS₄), niccolite (NiAs), arsenopyrite (FeAsS) and loellingite (FeAs₂). The NQR frequencies have been determined from both high-field NMR powder patterns and via zero-field frequency sweeps. Density functional theory (DFT) based ab initio calculations support the experimental results. The compounds studied here are common in terms of the known set of As-containing minerals. They are sometimes encountered in the context of base metal or gold mining. The study represents a significant addition to the list of arsenic minerals that can now be detected with NQR techniques.     

Cu chemistry of YBa2Cu3O6+x investigated by nuclear quadrupole resonance

The nuclear quadrupole resonance (NQR) technique has been utilized to characterize the local oxygen coordination of inequivalent Cu sites in YBa₂Cu₃O_6+x(0 ≤ x ≤ 0.91). Essentially, four distinct NQR lines which correspond to 2, 3,4 oxygen coordinated Cu sites in the Cu-O chains and 5 oxygen coordinated Cu sites in the Cu-O planes have been observed. The zero-field NQR frequencies of these are centered at about 30.1, 24.0, 22.0 and 31.5 MHz for ⁶³Cu, respectively. For the antiferromagnetic ordered state (x ≤ 0.3), antiferromagnetic nuclear resonance (AFNR) has been observed at 90 MHz with quadrupole splittings associated with the moment-bearing Cu sites in the Cu-O planes. The relative intensities of these resonance lines depend on the oxygen content, and this gives us a microscopic understanding of the Cu chemistry of this system.     

Sublevel spectroscopy of alkali atoms in superfluid helium

We report the results of optical pumping and optical detection of magnetic resonance of alkali atoms (Cs and Rb) in superfluid helium. The magnetic resonances between the ground-state Zeeman sublevels and hyperfine levels are observed through monitoring theD ₁ fluorescence by means of the optical-rf double resonance technique. Although the ground stateg values in superfluid helium are the same as in vacuum within the experimental error, the hyperfine constant of the ground state of the Cs atom in superfluid helium is found to be slightly larger than in vacuum. Coherent transient spectroscopy is also performed.     

La NMR and As NQR study of the As-based filled skutterudite LaOs4As12

We report experimental results of nuclear magnetic resonance (NMR) at the La site and nuclear quadrupole resonance (NQR) at the As site in the normal state of the superconducting compound LaOs₄As₁₂. Measurements have been performed on powder sample obtained from high quality single crystals. The temperature dependences of the nuclear spin-lattice relaxation rates, 1/T₁, of ⁷⁵As and ¹³⁹La nuclei were measured. No scaling between them was found indicating a local character of relaxation processes. The relaxation of ⁷⁵As nuclei can consistently be understood in terms of antiferromagnetic spin fluctuations, as deduced from the T-dependence of (1/T₁T)=C/(T−θ)^1/2.     

As-NMR/NQR study of pressure-induced superconductivity in CaFe2As2

⁷⁵As-zero-field nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements are performed on CaFe₂As₂ under pressure. At P=4.7 and 10.8 kbar, the temperature dependence of nuclear-spin-lattice relaxation rate (1/T₁) measured at tetragonal phase show no coherence peak just below T_c and decrease with decreasing temperature. The superconductivity is of gapless at P=4.7 kbar but evolves to multiple gaps at P=10.8 kbar. We find that the superconductivity appears near a quantum critical point. Both electron correlation and superconductivity disappear in the collapsed tetragonal phase. A systematic study under pressure indicates that electron correlations play a vital role in forming Cooper pairs in this compound.     

Correlation-based method for improvement of NQR signals utilizing signal shape information

In the correlation method the signal shape information can be utilized for detection of weak signals, hidden in the noise. We tested the advantages, drawbacks and some practical features of the method applied to magnetic resonance detection. The influence of the signal width, shape and similarity to the template on the correlation function was studied by numerical simulation. The findings were applied to the optimization of the template for improved localization of a noisy¹⁴N nuclear quadrupole resonance (NQR) line in NaNO₂ during repetitive scans by a superregenerative spectrometer. The value of the correlation method in faster NQR intensity evaluation was also confirmed.     

The two-frequency nuclear quadrupole resonance for explosives detection

The two-frequency nuclear quadrupole resonance (NQR) of¹⁴N nuclei is described for purposes of explosives detection. Two applications are known: two-frequency NQR for increasing the signal intensity, two-frequency NQR for improved reliability of explosives detection. The two-frequency experiments were carried out in hexahydro-1,3,5-trinitro-s-triazine C₃H₆N₆O₆ and sodium nitrite NaNO₂ as a substitute for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocycine C₄H₈N₈O₈. The two-frequency sequences for NQR are proposed for increasing the amplitude of NQR signal and improvement of detection condition.     

Static displacement of a guest atom in filled skutterudites MFe<Subscript>4</Subscript>Sb<Subscript>12</Subscript> (M = La,Ca, Na)

The properties of filled skutterudites MFe₄Sb₁₂ (M = La, Ca, Na) have been analyzed using the nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) methods. Two lines have been observed on the ¹³⁹La NMR spectrum of the LaFe₄Sb₁₂ compound and a substructure has been revealed in the ¹²¹Sb and ¹²³Sb lines in the NQR spectra of LaFe₄Sb₁₂ and CaFe₄Sb₁₂. The concept of the partial static displacement of guest atoms (M) in LaFe₄Sb₁₂ and CaFe₄Sb₁₂ has been proposed. The ab initio calculations confirm this assumption as well as give the displacement of a guest atom and indicate the absence of the splitting of the ¹³⁹La NMR line in the LaFe₄Sb₁₂ spectrum.     

Molecular motions in chloramphenicol studied by35Cl nuclear quadrupole and1H nuclear magnetic resonance spectroscopy

The³⁵Cl nuclear quadrupole resonance (NQR) frequency (v_Q), nuclear quadrupole spinlattice relaxation time (T_1Q),¹H nuclear magnetic resonance second moment (M₂) and nuclear magnetic spin-lattice relaxation timeT ₁) were measured for polycrystalline chloramphenicol (drug) as a function of temperature. Hindered rotation of the CHC1₂ group and the phenyl ring was detected, the relevant activation energies were determined. The rotations are discussed in detail.     

Hyperfine structure and nuclear magnetic moments of some neutron-deficient thallium isotopes

Using the atomic-beam magnetic resonance method, hyperfine structure (h.f.s.) measurements have been performed in the²P_1/2 electronic ground state of the neutron-deficient thallium isotopes^193–202Tl. In the doubly odd isotopes, the magnetic dipole hyperfine interaction constantsa were determined, while in the odd-A isotopes, direct measurements of the nuclearg-factors,g _I , were made. The electronicg-factor was measured in¹⁹⁸Tl. The magnetic dipole moments of the doubly odd isotopes have been evaluated by a direct comparison with known values in the stable isotope²⁰³Tl. The moments of the odd-A isotopes are in agreement with pervious measurements by optical spectroscopy. A discussion of the magnetic dipole moments in terms of different nuclear models is included. The moments of the 2^? nuclear ground states of the doubly odd isotopes may be interpreted as arising from a combination of the configurations 2^? (πs_1/2 vf_5/2) and 2^? (πs_1/2 vp_3/2).     

Nuclear spin induced collapse and revival shape of Rabi oscillations of a single electron spin in diamond

A collapse and revival shape of Rabi oscillations in an electron spin of a single nitrogen-vacancy centre has been observed in diamond at room temperature. Because of hyperfine interaction between the host ¹⁴N nuclear spin and the nitrogen-vacancy centre electron spin, different orientations of the ¹⁴N nuclear spins lead to a triplet splitting of the transition between ground state (m_s =0) and excited state (m_s =1). The manipulation of the single electron spin of nitrogen-vacancy centre is achieved by using a combination of selective microwave excitation and optical pumping at 532 nm. Microwaves can excite three transitions equally to induce three independent nutations and the shape of Rabi oscillations is a combination of the three nutations.     

γ-Detected NMR of103 mRhFe

Using the method ofγ-detection, the NMR in the metastable 40 keV-state of¹⁰³Rh in Fe (thin foils with diffused¹⁰³Pd activity) was measured in external fields of 0.5 to 14 kG. We find a zero-field resonance frequency ofv ₀=(550.3±0.5) MHz and a slope ofdv/dH= ?(0.933 ±0.017) MHz/kG, yielding g=1.22 ± 0.02. The resulting value for the hyperfine field, H_hf=(590±10) kG, is inconsistent with that of an NMR measurement in the ground state of¹⁰³Rh. Possible reasons for this discrepancy are discussed.     

Submillimeter-wave spectroscopy of VN (XΔr) and VO (XΣ): A study of the hyperfine interactions

The pure rotational spectra of VN (X³Δ_r) and VO (X⁴Σ⁻) have been recorded in the frequency range 290-520 GHz using direct absorption spectroscopy. These radicals were synthesized in the gas-phase from the reaction of VCl₄ with either N₂ or H₂O in an AC discharge. Seven rotational transitions were recorded for each molecule; in both sets of spectra, fine and hyperfine structures were resolved. The data sets for VN and VO were fit with Hund’s case (a) and case (b) Hamiltonians, respectively, and rotational, fine structure, and hyperfine constants determined. For VN, however, an additional hyperfine parameter, Δa, was necessary for the analysis of the Ω = 2 sublevel to account for perturbations from a nearby ¹Δ state, in addition to the usual Frosch and Foley constants. Determination of Δa suggests that the ¹Δ state lies ∼3000 cm⁻¹ above the ground state. In VO, the hyperfine structure in the F₂ and F₃ components was found to become heavily mixed due to an avoided crossing, predicted by previous optical studies to be near the N = 15 level. The hyperfine constants established for these two molecules are consistent with the proposed σ¹δ¹ and σ¹δ² electron configurations.     

Observation of the double optical-gamma resonance in Mössbauer spectra of 151 Eu in EuP 5 O 14 single crystal

A theoretical analysis has been made and calculation procedures have been developed for describing the hyperfine structure of ¹⁵¹Eu Mössbauer spectra and the effect of double optical-gamma resonance (DOGR) in the presence of hyperfine quadrupole interaction with an arbitrary symmetry of the electric field gradient tensor. An experimental setup was designed for DOGR-effect observation, incorporating the pumping argon laser and the tunable dye laser combined with the Mössbauer spectrometer on a common platform. The Mössbauer absorption spectra of ¹⁵¹Eu^3?+? nuclei in single crystals of europium pentaphosphate, EuP₅O₁₄, have been measured at T = 5 K and 80 K under the absence and presence of optical pumping tuned to the ⁷F $_{0}-^{5}$ D₀ electronic transition at the 578 nm wavelength. A simultaneous analysis of these spectra in terms of the spin Hamiltonian of hyperfine quadrupole interaction has allowed us to evaluate the DOGR-effect magnitude with the population of the excited (⁵D₀) electronic state under optical pumping of about 10 %.     

Nuclear quadrupole resonance echoes from hexamethylenetetramine

We investigated the echo phenomenon of nuclear quadrupole resonance (NQR) from hexamethylenetetramine (HMT). We detected the pure NQR echo signal of HMT with a short pulse interval. The intensity of the echo signal increased as the pulse interval time was decreased. We observed that a clean echo signal was generated even when the pulse interval was shorter than the decay time constant T₂^*. Since the short interval time gives a strong echo, our result insists that shorter interval time is preferred for the NQR detection.     

Analysis of hyperfine structure of Rare‐Earth Ions in Single Crystals by Electron Paramagnetic Resonance Spectroscopy

Electron paramagnetic spectroscopy of rare‐earth ions in single crystals is an interesting tool to analyze the hyperfine structure of the ground state of the rare‐earth. This can be useful for coherent spectroscopy and quantum information applications where the hyperfine structure of the electronic levels is used. Moreover, in some cases, the electron paramagnetic resonance hyperfine structure of interacting rare‐earth ions allows us to retrieve the isotropic exchange interaction between the two interacting ions. We illustrate these points with the hyperfine structure of Yb³⁺ ions in vanadate crystals, the hyperfine structure of Er³⁺ ions in Y₂SiO₅, and the hyperfine structure of Yb³⁺ pairs in CsCdBr₃.     

Impurity-induced magnetic order in the mixture of two spin gap systems (CH3)2CHNH3CuCl3 and (CH3)2CHNH3CuBr3

The ground state of the solid solution of the two spin gap systems (CH₃)₂CHNH₃CuCl₃ and (CH₃)₂CHNH₃CuBr₃ has been investigated by ¹H NMR. The existence of a magnetic ordering in the sample with the Cl-content x=0.85 was clearly demonstrated by a drastic splitting in a resonance line at low temperatures below T_N=13.5 K. The observed NMR spectra in the ordered state was qualitatively consistent with the simple antiferromagnetic state.