Pulsed 14N NQR Device Designed to Detect Substances in the Presence of Environmental Noise

A new device designed for both volumetric and surface NQR detection of substances spatially located in several positions, and in the presence of environmental interference, is described. The device consists of two probe coils, placed on the same detection plane, for excitation and detection of NQR signals. Experimental results obtained using Strong Off Resonance Comb (SORC) pulse sequences, for the excitation of the ν- transition in samples of Sodium Nitrite (NaNO ₂), are presented. It is shown that, when the total signals induced in each coil are properly combined, the interference commonly detected in both coils is attenuated relative to the NQR signal detected by either one or both probe coils. NQR signal can be detected by either one or both coils, but in both cases the noise induced by distant environmental sources is attenuated. These files correspond to the revised version of the paper N° O-G-6, entitled “Pulsed ¹⁴N NQR device designed to detect substances in the presence of environmental noise” presented at the XVII International symposium on Nuclear Quadrupole Interactions, held in Bonn, Germany in 2004. Argentinian and International patents pending.     

Nuclear quadrupole resonance studies of209Bi in Bi4(GeO4)3 and Bi4(SiO4)3

Nuclear quadrupole resonance (NQR) of²⁰⁹Bi has been studied in Bi₄ (GeO₄)₃ and Bi₄ (SiO₄)₃ using a wide band coherence-controlled superregenerative oscillator-detector. All the four allowed (ΔM _I=±1) transitions are observed. In both cases the electric field gradient (EFG) tensor is axially symmetric (η=0.0). The quadrupole coupling constante ² qQ is measured to be 490.8±1 MHz and 470.4±1 MHz respectively. It is pointed out that the purely ionic model is inadequate to understand these results. With the available experimental accuracy and the strength of the applied electric field (∼ 6 KV/cm), no field-induced effects on the NQR spectrum could be observed in the case of Bi₄ (SiO₄)₃.     

121Sb and 123Sb NQR and the heterophase structure in the SbSI ferroelectric

The temperature dependences of NQR line frequencies and widths of ¹²¹Sb (for the ±1/2→±3/2 transition) and of ¹²³Sb (for the ±1/2→±3/2 and ±3/2→±5/2 transitions), as well as of the principal components and the asymmetry parameter of the electric-field-gradient tensor at the ¹²³Sb nucleus have been studied in a SbSI crystal in the 115–325 K range. The dynamic and static factors governing the character of these relations are discussed. The ±1/2→±3/2 line in the ¹²¹Sb NQR spectrum splits into a doublet within a narrow (0.5 K) temperature interval near the ferroelectric phase transition (T _c=293 K), which is associated with the formation of a macroscopic heterophase structure in the crystal. Fiz. Tverd. Tela (St. Petersburg) 41, 1286–1292 (July 1999)     

Hyperfine Interactions of N Isotopes in TiO2 and Quadrupole Moment of 16N

Hyperfine interactions of ^12,14N in BN(hexagonal) crystal were studied by detecting β-NQR(¹²N) and FT-NMR(¹⁴N). A β-NMR of ¹⁶N (I ^π=2⁻,T _1/2=7.13 s) in MgO crystal was detected to determine the magnetic moment of ¹⁶N to be |μ(¹⁶N:2⁻)|=(1.986±0.001)μ_N. Also, the β-NQR of ^12,16N in TiO₂ crystal were detected to determine |Q(¹⁶N:2⁻)|=(17.9±1.7) mb. An abnormally small effective charge for neutrons is required to account for |Q(¹⁶N:2⁻)|. This revised version was published online in September 2006 with corrections to the Cover Date.     

14N NQR study of selected 1,4-benzoquinonedioximes

The ¹⁴N NQR frequencies of selected 1,4-benzoquinonedioximes were measured using cross relaxation double resonance. As the number of substituents increase, a significant shift in the NQR values is observed. Comparison of unsubstituted and tri-substituted 1,4-benzoquinonedioximes shows that the quadrupole coupling constant (χ) increases by about 1000 kHz and the asymmetry parameter (η) decreases from ≈0.7 to 0.3 respectively. Ab-initio calculations show that for the unsubstituted compound hydrogen bonding between oxime groups and pi-ring stacking is possible which cannot be accommodated for in heavily methyl substituted dioximes and this results in distinct NQR parameters.     

Nuclear Spin–Lattice Relaxation of Single Crystal Sr14Cu24O41

Nuclear spin–lattice relaxation rate T ₁ ⁻¹ has been measured for the ladder sites of two single crystals Sr₁₄Cu₂₄O₄₁ (Sr14-A,B) by ⁶³Cu NMR/NQR. The hole localization around 100 K appears as a peak in the T variation of T ₁ ⁻¹(NQR). On the other hand, it is suppressed in the T ₁ ⁻¹ (NMR) data under the magnetic field H ∼ 11 T, and a new peak appears around 20 K. T ₁ ⁻¹(NMR) around the peak is more enlarged for Sr14-B than for Sr14-A. Hence, holes on the ladders of Sr14-B tend to be more localized. This is considered to be an origin for the occurrence of the magnetic order in Sr14-B under H ∼ 11 T.     

Transitions and Spin Dynamics at Very Low Temperature in the Pyrochlores Yb2Ti2O7 and Gd2Sn2O7

An orientational disorder of the cation in [(PyO)D][AuCl₄] crystal was investigated by the ³⁵Cl NQR and ¹H NMR measurements. A structural phase transition was found at ca. 70 K from the temperature dependence of the NQR frequencies both in [(PyO)D][AuCl₄] and [(PyO)H][AuCl₄]. Temperature dependence of the spin-lattice relaxation time T ₁ of the NQR of [AuCl₄]⁻ could be interpreted by an electric field gradient modulation due to the motion of the cation. Characteristics of T ₁ of ³⁵Cl NQR as well as that of ¹H NMR suggest a dynamic orientational disorder of the cation.     

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.     

NQR Study of Phase Transition and Cationic Motion in 4-NH2C5H4NHBiBr4·H2O

Four ⁸¹Br NQR lines in 4-NH₂C₅H₄NHBiBr₄·H₂O were observed in the temperature range between 77 and ca. 380 K; with increasing temperatures the respective sets of higher and lower two resonance lines coalesced into single lines discontinuously at 274 K, showing the occurrence of a first-order type phase transition of this crystal. The transition was confirmed with heat anomaly on a DTA curve. Each higher and lower line of high-temperature phase is assignable to the terminal Br atoms and the bridging ones of one-dimensional poly anions (BiBr₄ ⁻) _n in the crystal structure (C2/c), which was investigated by a X-ray structure analysis at room temperature. The 1/T ₁ temperature dependence of ⁸¹Br NQR follows the usual T ² law in the temperature range between 77 and ca. 140 K, being explained by fluctuation of the EFG at Br nucleus due to lattice vibrations. The T ₁ vs. 1/T curve in the temperature range between about 160 and 190 K was describable by the exponential curves, allowing us the estimation of activation energies. These exponential behaviors of T ₁ of ⁸¹Br NQR are attributable to the fluctuations caused by the thermal motion of 4-NH₂C₅H₄H⁺ ions. Echo signals of the ⁸¹Br NQR could not be detected above 190 K owing to poor S/N with very short T ₂.     

Precise measurement of magnetic moment of short-lived β-emitting nuclei12B ( I π=1+, T 1/2=20.18 ms)

The spin polarized β-emitting nuclei¹²B (I ^π=1⁺,T _1/2=20.18 ms) were produced by the nuclear reaction¹¹B(d, p)¹²B and by the selection technique of the incident deuteron energy and the¹²B recoil angle following the nuclear reaction. The nuclear magnetic moment of the short-lived nuclei¹²B was measured by β-NMR with the β-NMR and β-NQR setup established for the first time in China. The nuclear magnetic moment of¹²B was determined to be μ=0.99993±0.00048 nm org=0.99993±0.00048 after the precise correction of the Knight shift.     

New Methods for Detection of 14N NQR Frequencies

Nitrogen atoms are present in a number of solid explosives and illicit substances. The nuclear quadrupole resonance (NQR) spectra and spin?Clattice relaxation of the nitrogen atomic nucleus ¹⁴N can be used to characterize these compounds and to distinguish between possible crystal polymorphs. After the characteristic ¹⁴N NQR frequencies and spin?Clattice relaxation rates in a compound are determined, NQR can be used to detect this compounds and, in case of crystal polymorphs, also to determine the method of preparation. The ¹⁴N NQR frequencies and spin?Clattice relaxation rates are measured either by pulse NQR or by nuclear quadrupole double resonance (NQDR) based on magnetic field cycling. Here, we discuss several ¹H?C¹⁴N NQDR techniques which can be used to measure the ¹⁴N NQR frequencies and spin?Clattice relaxation rates under various experimental conditions. Some characteristic applications of these techniques are presented and discussed in details.     

NQR, NMR and Crystal Structure Studies of [C(NH2)3]2HgX4 (X = Br, I)

The crystal structure of [C(NH₂)₃]₂HgBr₄ has been determined at room temperature: monoclinic, space group C2/c, with a = 10.035(2), b = 11.164(2), c = 13.358(3) Å, β = 111.67(3)°, and Z = 4. The crystal consists of planar [C(NH₂)₃]⁺ and distorted tetrahedral [HgBr₄]^2? ions. The Hg atom is located on a two-fold axis such that two sets of inequivalent Br atoms exist in an [HgBr₄]^2? ion. In accordance with the crystal structure, two ⁸¹Br NQR lines widely separated in frequency were observed between 77 and ca. 380 K. [C(NH₂)₃]₂HgI₄ yielded four ¹²⁷I NQR lines ascribable to m = ±1/2 ? ±3/2 transitions, indicating that its crystal structure is different from the bromide complex. The ¹H NMR T ₁ measurements showed a single minimum for the bromide but two minima for the iodide. The analyses based on the C₃ reorientations of the planar [C(NH₂)₃]⁺ ions gave the activation energies of 29.8 kJ mol^?1 for the bromide, and 30.2 and 40.0 kJ mol^?1 for the iodide.     

T1? in nuclear quadrupole resonance: a theoretical study

A new NQR method of measuring the spectral density of slow motions in solids is proposed. It is shown that also in NQR a 90 ° phase shift of a resonant rf magnetic field following a 90 ° pulse locks the nuclear magnetization in a ‘rotating frame’ similarly as in NMR. The spin-lattice relaxation time T_1? of the locked magnetization is calculated in general for an arbitrary spin. It is assumed that the fluctuations of the EFG tensor dominate the spin-lattice relaxation. The calculations show that T_1? depends on the spectral density J(ω) of the electric quadrupole fluctuations at the NQR frequencies, and also at a low frequency Ω. Here kHz depends on the orientation of the rf magnetic field in the principal-axis system of the EFG tensor. The term containing in the expression for T_1?⁻¹ depends on the orientation of the rf magnetic field in the principal-axis system of the EFG tensor, only through the orientation dependence of Ω. This term vanishes when the electric quadrupole fluctuations do not modulate the frequency of the NQR transition excited by the rf magnetic field. Two particular examples: are worked out in details.     

Improving N nuclear quadrupole resonance detection of trinitrotoluene using off-resonance effects

The off-resonance dependence of the amplitudes of the six dominant ¹⁴N nuclear quadrupole resonance (NQR) lines in commercial polymorphic trinitrotoluene (TNT) sample were experimentally determined for a wide range of experimental parameters when irradiated with the spin-lock spin-echo (SLSE) pulse sequence. We find that the amplitudes off-resonance dependence follows a sinc-like function with an additional modulation due to the spacing between the RF pulses. This dependence can be very well modeled with expressions we have derived for a single site ¹⁴N NQR in paranitrotoluene (PNT). The results can be immediately used for the reduction of the number of free parameters used in the robust signal processing models for the TNT NQR detectors.     

Reflection asymmetry in the structure and spectroscopy of224Ac

Minor changes in the assignments of gamma rays following the alpha decay of²²⁸Pa in two previous studies make possible a reinterpretation of²²⁴Ac into two alternative level schemes. The resulting level structures arise from the reflection asymmetric configurations π3/2^±(0.0 −0.3)−ν3/2^±(−0.1 0.6), π5/2^±(0.0 −0.2)±ν3/2^±(−0.1 0.6) and π5/2^±(0.0 −0.2)±ν1/2^±(0.2 −0.1 3) which give rise to eitherK=0^± or 1^±,K=4^±,K=2^± andK=3^± parity doublet bands. The bands with appreciable band structure, namelyK=0^± or 1^± andK=3^±, have average parity doublet splittings of 11.0 and 5.8 keV respectively. These are extremely small values and suggest that²²⁴Ac is the most octupole deformed nucleus studied thus far. A method of calculating the parity doublet splitting in odd-odd nuclei is suggested and tested for²²⁴Ac. It seems to work remarkably well. The systematics of the hindrance factors for the bands with extended band structures confirm their interpretations as band structures. Finally, the two alternative level schemes are analyzed in the framework of the axially-symmetric rigid rotor model including the Coriolis interaction.     

The Effect of Biocompatible Coating Layers on Magnetic Properties of Superparamagnetic Iron Oxide Nanoparticles

The g-factor of the exteremely proton-rich nucleus ²³Al(T _{1 / 2} = 0.47 s) has been measured for the first time, applying β-NMR technique on this nucleus implanted in Si. The obtained ∣g∣ = (1.58 ± 0.2) suggests that the spin of the ground state of ²³Al is 5 / 2. The magnetic moment is determined as ∣μ∣ = (3.95 ± 0.55) μ _N .     

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.     

Measurement of the Magnetic Moment of the First Excited State in 93Sr Using on-line TDPAC technique

The g-factor of the first excited state of ⁹³Sr (E = 213 keV, T _1/2 = 4.6 ns) was measured by an on-line TDPAC technique with use of the strong hyperfine field in Fe metal. The Larmor frequency ω _L = (2.60 ± 0.15) × 10⁸ rad/s was obtained. The g-factor is derived as g = −0.227 ± 0.013 from g = −ℏω _L/B _hf μ _N. If the spin of the first excited state of ⁹³Sr is assumed to be 3/2, the g-factor is predicted by a simple core-excitation model as g = −0.22, which is in good agreement with the present experimental result.     

NQR frequencies in polycrystalline samples and their correlation with σ and k i values

NQR frequencies are studied in 6 compounds at 77°K and room temperature. The frequencies of the substituted chlorobenzene derivatives are compared with values calculated using the σ andk values of Hammett and Biedenkapp and Weiss respectively. The poor agreement between observed and calculated values is ascribed to the presence of two or more substituent groups other than chlorine and the consequent interaction between them. The poor agreement with Nagarajan’s equation at room temperature is ascribed to the increase in temperature. The σ andk values for the orthobenzamide group are estimated from the observed frequencies as 0.275 and 0.369 respectively.     

Precise Quadrupole Moment of the Doubly Closed Shell Plus One Proton Nucleus 41Sc

In order to precisely determine the |eqQ(⁴¹Sc)/h| of ⁴¹Sc(I ^π=7/2⁻, T _1/2=0.596 s) implanted in a TiO₂ single crystal the electric field gradient tensor and anisotropic chemical shift were determined by detecting the Fourier Transformed Pulse-NMR of ⁴⁵Sc(I ^π=7/2⁻, stable) in the crystal at a high field of 7.0 T and 9.4 T. Combining the new |eqQ(⁴¹Sc)/h| value with the Q(⁴⁵Sc)=−(23.6±0.2) fm², also renewed by using the known atomic hyperfine interaction constants and Sternheimer polarization effect, the |Q(⁴¹Sc;I ^π=7/2⁻,T _1/2=0.596 s)|=(15.6±0.3) fm² has been precisely determined. The value is compared with the theoretical Q(⁴¹Sc) given by a shell model code. This revised version was published online in September 2006 with corrections to the Cover Date.