19F N.M.R. and 127I N.M.R. and N.Q.R. study of the molecular motions and deformations of iodine heptafluoride in its solid phases

In solid IF₇, ¹⁹F and ¹²⁷I N.M.R. and ¹²⁷I N.Q.R. absorption line shapes, frequencies and relaxation times have been studied from the melting temperature down to 56 K. Two new solid-solid transitions have been found at 180 K and 96 K in addition to the one already known at 153 K. The two high temperature phases are shown to be plastic. The fast molecular rotations and the slow molecular diffusion are studied from ¹⁹F and ¹²⁷I relaxation times. In the ordered phases, an analysis of the ¹⁹F second moments and longitudinal relaxation times shows the existence of a fast intramolecular exchange between axial and equatorial fluorine atoms, together with a much faster reorientation about the D ₅ axis. The characteristic times of these two motions are obtained and a mechanism for the exchange process is proposed. The chemical shift values of ¹²⁷I, the temperature dependence of the N.Q.R. frequencies and of the N.Q.R. relaxation times of ¹²⁷I, as well as the dipolar energy relaxation times have been measured and are discussed.     

Nuclear quadrupole interaction in the low dimensional hf-trichalcogenides

We report on Time Differential Perturbed Angular Correlation measurements of the nuclear quadrupole interaction of¹⁸¹Hf(β⁻)¹⁸¹ and its temperature dependence in the low dimensional Hf- trichalcogenides HfS₃, HfSe₃ and HfTe₃. In HfS₃ the temperature dependence of the precession frequency is a slowly decreasing function with a negative curvature, the deviation from axial symmetry of the electric field gradient is practically temperature independent. In HfSe₃ the NQI shows a peculiar behaviour; between 10K and 300K the quadrupole frequency and the asymmetry parameter increase, between 300K and 400K the frequency decreases while the deviation from axial symmetry increases, indicating a structural phase transition near room temperature. In HfTe₃ the quadrupole frequency is practically temperature independent below 600K and increases linearely at higher temperatures, the asymmetry parameter increases steadily in the temperature range from 10K to 600K and then decreases. There is a strong correlation between the strength and the asymmetry of the electric field gradient so that the system depends on one control parameter only.     

N.M.R. studies of liquid boron trifluoride

Previous ¹⁹F N.M.R. studies of liquid BF₃ have been extended by obtaining the ¹¹B spectrum of BF₃ and the ¹⁹F spectrum of ¹⁰BF₃ at various temperatures. Values for the B-F coupling constant and the boron relaxation times have been obtained by computer matching and visual matching of observed and calculated spectra. Relaxation times have the Arrhenius temperature dependence found previously. The temperature dependence of the B-F coupling constant is discussed. Some of the possible advantages of ‘high spin spectra’ are discussed.     

Hyperfine Interactions in the Sr0.88Ba0.12HfO3 Compound

The temperature dependence of the hyperfine parameters in a powder sample of the Sr_0.88Ba_0.12HfO₃ compound has been investigated for the first time using perturbed angular correlation spectroscopy. The time spectra were measured as a function of the temperature from 293 to 1273 K. Activated ¹⁸¹Ta nuclei were used as hyperfine probes at the Hf sites. The analysis of the time spectra indicates the presence of two different surroundings for the Ta probes. The most populated site (f ₁≈75% at laboratory temperature) was fitted with the usual static quadrupole hyperfine interactions found in most perovskite-type compounds. The resulting quadrupole frequency is ω _Q ≈24 Mrad/s at this temperature. This frequency continuously decreases to nearly 9 Mrad/s at 1273 K. Its line width temperature dependence displays three regions and the changes observed probably correspond to phase transitions. The other site has a large and temperature independent quadrupole frequency ω _Q ≈120 Mrad/s that reversibly transforms into the first at high temperatures and probably originates from some defect in the structure. This revised version was published online in September 2006 with corrections to the Cover Date.     

Anomalous temperature dependence of the quadrupole coupling frequency of a lattice defect trapped to111In in Pt

The quadrupole coupling frequency of an¹¹¹In-defect bound state in Pt with ω₀(295 K) = 200 Mrad/s was measured over the range 4 – 300 K using perturbed angular correlations. The temperature dependence exhibited positive curvature, unlike the T^3/2 dependence observed in noncubic metals, and was fitted using a model which assumed that the temperature dependence was caused by vibrations of a resonant mode in the probe-defect complex.     

Studies of molecular dynamics of thiazides by<Superscript>35</Superscript>Cl NQR spectroscopy and DFT calculation

Molecular dynamics of three derivatives of 1,2,4-benzothiadiazine-1,1-dioxide, hydrochlorothiazide (HCTZ), althiazide (ATZ) and chlorothiazide (CTZ), was studied by³⁵Cl nuclear quadrupole resonance (NQR) spectroscopy. The temperature dependence of the resonance frequency was analyzed within the 6 known standard models. The activation energies estimated from the temperature dependence of the³⁵Cl NQR frequency assuming the Bayer model were 1.07, 2.35 and 2.76 kJ/mol for HCTZ, ATZ and CTZ respectively, which confirms that HCTZ is less rigid than CTZ and ATZ is much more rigid than HCTZ, and suggests that the mechanism of relaxation is based on small amplitude librations. The characteristic temperatures estimated from the Bayer model, with that for CTZ (332.5 K) being much higher than for HCTZ (132.1 K), mean that the intermolecular interactions in CTZ are much stronger than in HCTZ, as suggested by the melting point of CTZ being higher than that for HCTZ. For ATZ the characteristic temperature (288 K) takes an intermediate value, which suggests that the intermolecular interactions in this compound are stronger than in HCTZ and weaker than in CTZ. A significant narrowing of the resonance³⁵Cl NQR line observed for all these compounds at room temperature, relative to that at the liquid nitrogen temperature, suggests an averaging of dipolar interactions as a result of fast rotation of nonquadrupole nuclei in the vicinity of the quadrupole nuclei, when 2πν_Qτ_c ≫ 1 (a rotation of the −NH₂ group in the direct neighborhood of the chlorine nuclei) or a change in the gradient orientation with its value preserved (which is equivalent to rotation of the quadrupole nucleus Cl). The influence of the rotations of the −NH₂ and −CH₂SCH₂CH=CH₂ groups (ATZ) or −CHCl₂ group (TCTZ) on the³⁵Cl NQR frequency was modelled by the B3LYP/6-31G^* method. The frequencies of the libration vibrations calculated from the temperature dependence of the NQR resonance frequency were compared with experimental ones and those implied by the density functional theory, infrared and Raman spectra. For HCTZ the anomalies in the temperature dependence of the³⁵Cl NQR frequency, the lack of hysteresis and small but notable changes in the slope and the jump in the frequency observed at 253 K which does not exceed 0.05 MHz suggest a second-order phase transition at 253 K.     

Magnetic and quadrupole interaction studies at 111Cd in GdMn2 and TbMn2

The temperature dependence of the electric quadrupole interaction and the magnetic hyperfine field at ¹¹¹Cd probe sites in RMn₂ (R=Gd, Tb) has been studied by TDPAC method. In the paramagnetic region the quadrupole interaction frequency ν_Q in both compounds varies linearly with temperature. Below the Neel temperature, we find an abrupt decrease in the magnitude of ν_Q which is consistent with an expansion of the unit cell. As an important feature, the data near T_N shows the coexistence of localized and itinerant magnetism of Mn atoms. This revised version was published online in August 2006 with corrections to the Cover Date.     

Temperature dependence of17O and14N NQR frequencies in commercial TNT

The temperature dependence of the¹⁷O nuclear quadrupole resonance (NQR) frequencies has been measured in commercial trinitrotoluene by highly sensitive nuclear quadrupole double resonance techniques. The¹⁴N NQR frequencies have been measured in the same sample for comparison. In contrast to the¹⁴N quadrupole coupling constant, the¹⁷O quadrupole constant increases with increasing temperature.     

Nuclear quadrupole resonance of norephedrine

Toward searching for illegal drugs, we investigated the pulsed nuclear quadrupole resonance (NQR) response of ¹⁴N in (1R,2S)-(-)-norephedrine, based on the predictions of quantum chemical calculations. Two pairs of spectral lines (ν₊=3.089, 3.093 MHz and ν₋=2.594, 2.608 MHz) were observed despite its molecule structure having only a single nitrogen atom. This indicates that the molecular crystal has two nonequivalent nitrogen atoms in the unit cell. The temperature dependence of the NQR frequencies and relaxation properties were investigated for the purpose of accurate remote sensing of the drugs. The NQR frequency shift was approximately 0.23 kHz/K around room temperature. The spin-lattice relaxation and spin-phase memory times were 5.2–10.2 ms and 0.6–1.5 ms, respectively.     

Hyperfine interactions at R and In sites in RNiIn (R = Gd, Tb, Dy, Ho) compounds measured by perturbed angular correlation spectroscopy

Perturbed gamma–gamma angular correlation (PAC) technique was used to measure the magnetic hyperfine field (mhf) in RNiIn (R = Gd, Dy, Tb, Ho) intermetallic compounds using the ¹¹¹In→¹¹¹Cd and ¹⁴⁰La→¹⁴⁰Ce probe nuclei. The PAC spectra for ¹¹¹Cd measured above magnetic transition temperature show a major fraction with a well defined quadrupole interaction for all compounds except GdNiIn where a single frequency was observed. PAC measurements below T _C showed a combined electric quadrupole plus magnetic dipole interaction for ¹¹¹Cd probe at In sites, and a pure magnetic interaction for ¹⁴⁰Ce at R sites. The temperature dependence of mhf measured with ¹⁴⁰Ce at R sites shows that the values of fields drop to zero at temperatures around the expected T _C for each compound. However, in the measurements with ¹¹¹Cd at In sites, the mhf values become zero at temperatures which are smaller than T _C . The difference between the temperatures at which mhf is zero for ¹⁴⁰Ce and ¹¹¹Cd probes correlates with T _C . For each compound this difference decreases with T _C . The results are discussed in terms of the RKKY model for magnetic interactions and the existence of two magnetic systems, with distinct exchange interaction energies due to different types of atomic layers in these compounds.     

Hydrogen-bonded ferroelectrics: Evidence for Slater configurations from E.P.R. studies of X-irradiated KH2AsO4 and NH4H2AsO4

The temperature dependence of the powder E.P.R. spectrum of the AsO₄ ^4- centre in x-irradiated samples of KH₂AsO₄ and NH₄H₂AsO₄ yields results which can be understood as arising from exchange processes taking place between the six configurations in the Slater model for this type of hydrogen-bonded ferroelectric and antiferroelectric. Knowing that the ⁷⁵As hyperfine parameters have rhombic symmetry in the compounds studied, it is possible to interpret certain specific features in the spectra as being associated with the Slater configurations of higher energy.     

Electronic structure and lattice dynamics of domeykite Cu<Subscript>3</Subscript>As according to nuclear quadrupolar resonance of<Superscript>75</Superscript>As and<Superscript>63,65</Superscript>Cu

The temperature dependences of nuclear quadrupole resonance (NQR) frequencies, the line width and nuclear relaxation of⁷⁵As and^63,65Cu, as well as the electrical resistivity in domeykite Cu₃As are studied in the temperature range of 4.2-300 K. The comparison of the calculated with the measured lattice contribution to the NQR frequencies points at a substantial role played by the conduction electrons in creating the electric field gradient at the nuclei sites. The temperature dependence of the copper and arsenic nuclear spin-lattice relaxation linear at 4.2<T<200 K and that of the electric resistivity (30<T<200 K) prove the metallic character of the conductivity of domeykite. The enhancement of nuclear relaxation, the narrowing of copper and arsenic NQR line widths are considered as arising due to the ionic movement starting beyond 200 K. This movement influences the electric resistivity, most likely due to the inreasing density of states at the Fermi surface.     

Electric-quadrupole interaction at 181Ta in f.c.t. ZrHi1.97

Time-differential perturbed γ-ray angular correlation experiments have been carried out on ¹⁸¹Ta impurities in ?-phase zirconium hydride over the temperature range from 20 to 588 K. A static, slightly asymmetric electric quadripole interaction is found at all temperatures. The static nature of the pattern indicates the absence of significant hydrogen diffusion at these temperatures on the time scale of the experiment (0.1 μsec). The temperature dependence of the static quadrupole frequency is given by the relation v_q(t) = 130[1 ? (1.9 × 10^?5)T^1.5] MHz.     

Orbital pair theory of N.M.R. shielding

A simple correction accounting for the effect of truncating the atomic orbital basis on the calculation of N.M.R. shielding is proposed. This correction is obtained from the expression for the magnetic shielding as a sum of orbital pair contributions: a spurious term that vanishes only if a complete basis is used appears in this expression. It is demonstrated both theoretically and numerically (using the example of PH₃) that removing this term from the results obtained with a truncated basis improves significantly the agreement with the experimental values. As a by-product the gauge dependence of the numerical results is much reduced. The additional computing time is negligible.     

A 2H and 14N NMR study of molecular motion in polycrystalline choline salts

²H and ¹⁴N solid-state NMR spectra of polycrystalline choline chloride, bromide, and iodide indicate that 180° cation flipping motion occurs in all three salts. From the temperature dependence of these spectra, the activation energy for this motion is determined to be 5.8 ± I kcal/mol in the iodide salt and 11 ± 1.5 kcal/mol in the chloride salt. In the bromide salt the reorientation rate is too rapid to be determined from the NMR lineshape, but the temperature dependence of the ²H quadrupole coupling parameters is indicative of a second-order phase transition at approximately 273 K. The spectral distortions in the ¹⁴N NMR spectra of the chloride and iodide salts are adequately explained using the motional model derived from the ²H NMR results, while the ¹⁴N spectra of the bromide salt show no motional effects. The axis of reorientation which is inferred from these data appears to be consistent with that indicated in a previous X-ray crystallographic study.     

Temperature dependence of79BrNQR frequency in cadmium strontium,barium, zinc,magnesium and nickel bromates

The⁷⁹Br quadrupole resonance in cadmium, strontium, barium, zinc, magnesium and nickel bromates is studied in the range 77 to 305 K. The temperature dependence of the resonance frequencies in these systems has been analysed on the basis of the torsional motion of the BrO ₃ ⁻ groups. The torsional frequency and its temperature behaviour have been analysed.     

The electric field gradient and its temperature dependence at111Cd in α-Uranium

The magnitude and temperature dependence of the quadrupole interaction at the¹¹¹Cd site in orthorhombic -Uranium was investigated between 293 and 17 K. The parent activity¹¹¹In was implanted into Uranium metal with an energy of 80 keV and the - TDPAC technique, applied to the 245 keV state in¹¹¹Cd, was used to measure the quadrupole interaction frequency. The derived electric field gradient for Cd in Uranium was found to be highly asymmetric (=1) and led to a quadrupole interaction frequency of _Q=7.10(7) MHz at 293 K. The temperature dependence of the quadrupole interaction is very strong, _Q increases to 14.3(2) MHz at 17 K and shows a linear dependence on the temperature.This work has been partially supported by the BMFT, FRG (03B01B0N/2).Work performed under the auspices of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under contract number W-7405-ENG-48.     

N.M.R. relaxation time studies in liquid methyl iodide

The spin-lattice relaxation times of the various nuclei in methyl iodide, methyl iodide-d ₃, and carbon-13 methyl iodide (¹³C, ¹H, ²D) were measured between 210 and 350 K. The separation of the proton-proton intermolecular relaxation was accomplished by a dilution study in methyl iodide-d ₃; the resulting intermolecular contribution agreed well with the existing theories for this mechanism. It was found that the spin-rotation interaction contributed significantly to the intramolecular relaxation of both the protons and the carbon-13. For both nuclei the separation of the spin-rotation interaction from the intramolecular dipole-dipole interaction was accomplished without making any assumptions about the temperature dependence of the spin-rotation relaxation time. The resulting spin-rotation relaxation times for both carbon-13 and protons offer evidence that the large spin-rotation effects are due to the methyl group reorientation.     

Temperature dependence of the quadrupole interaction of100Rh in a Cd lattice

The quadrupole interaction frequency |v _q| = |eQV _zz /h|0 = 8.71 ± 0.11 MHz was measured for the 75 keV state of¹⁰⁰Rh in a polycrystalline cadmium matrix by use of the γ-e^? and γ-γ time differential perturbed angular correlation (TDPAC) techniques. The temperature dependence of the electric quadrupole coupling constant for¹⁰⁰Rh in Cd is similar to those of other impurities in Cd metal.     

Linear temperature dependence of the electric quadrupole interaction of111Cd impurities in holmium

The electric quadrupole interaction of¹¹¹Cd impurities in metallic holmium has been investigated between 140 K and 655 K by time differential perturbed angular correlation measurements. The quadrupole frequency decreases with increasing temperature. This decrease is a linear function of temperature, in contrast to theT ^3/2 dependence usually observed in non-cubic metals. Possible reasons for the deviation from theT ^3/2 relation are discussed.