Double resonance experiments in low magnetic field: Dynamic polarization of protons by N and measurement of low NQR frequencies

The possibilities of dynamically polarizing proton spin system via the quadrupole ¹⁴N spin system in low magnetic field are analyzed. The increase of the proton magnetization is calculated. The polarization rate of the proton spin system is related to the transition probabilities per unit time between the ¹⁴N quadrupole energy levels and proton energy levels. The experiments performed in 1,3,5-triazine confirm the results of the theoretical analysis. A new double resonance technique is proposed for the measurement of nuclear quadrupole resonance frequencies ν_Q of the order of 100 kHz and lower. The technique is based on magnetic field cycling between a high and a low static magnetic field and observation of the proton NMR signal in the high magnetic field. In the low magnetic field the quadrupole nuclei and protons resonantly interact at the proton Larmor frequency ν_H = ν_Q/2. The quadrupole nuclei are simultaneously excited by a resonant rf magnetic field oriented along the direction of the low static magnetic field. The experimental procedure is described and the sensitivity of the new technique is estimated. Some examples of the measurement of low ¹⁴N and ²H nuclear quadrupole resonance frequencies are presented.     

Nitrogen-14 nuclear quadrupole resonance (NQR): dramatic sensitivity enhancement by large and fast temperature lowering

We have observed that, when going rapidly from ambient temperature down to liquid nitrogen temperature, the nitrogen-14 NQR signal (for transitions involving the m=0 spin state, nitrogen-14 being a quadrupolar nucleus of spin I=1) is increased by a factor of ca. 10(2). While Boltzmann statistics cannot explain this enhancement, the strong temperature dependence of the quadrupolar interaction is very likely to be at the origin of this phenomenon. Indeed, the quadrupolar Hamiltonian becomes time dependent and is prone to induce transitions toward the spin state associated with m=0. Its binding and slow relaxing properties result in a durable increased population and consequently in an increased intensity of NQR lines originating from the state m=0.     

14N pulsed nuclear quadrupole resonance. 3. Effect of a pulse train. Optimal conditions for data averaging

The calculations developed in this paper aim at determining the optimal conditions of a NQR experiment when a transition is monitored by means of a pulse train with pulses of identical duration and signal acquisition after each pulse; coherences are assumed to vanish by effective transverse relaxation prior to every new pulse. These calculations demonstrate that, as in NMR, a steady state is effectively reached for any value of the recycle time. However, by contrast with NMR, it is shown that, for optimal data averaging under steady state conditions, the recycle time T can be kept as low as possible (the only limitation is the acquisition time). Nutation curves (signal amplitude versus pulse length) calculated in the steady state case are shown to depend strongly on the ratio T/T ₁ (T ₁: longitudinal relaxation time). The signal growth as a function of T/T ₁under averaging of the first transients has been evaluated as well as the number of pulses necessary for reaching a steady state.     

Secondary signals in two-frequency nuclear quadrupole resonance on (14)N nuclei with I=1

Our experimental and theoretical studies show that using two-frequency excitation of (14)N nuclei it is possible to observe secondary NQR signals at one of the three possible transitions due to irradiation of another adjacent transition. As a result of the pulse sequence applied to the adjacent transition the spin-echo signals on the detected transition are observed after essential time interval from the initial single pulse on this frequency. Experiments have been performed on the (14)N nuclei in the sodium nitrite (NaNO(2)) and the military explosive hexahydro-1,3,5-trinitro-s-triazine C(3)H(6)N(6)O(6) (RDX).     

14N Pulsed nuclear quadrupole resonance. 4. Two-pulse sequences for the determination of T1 and T2 relaxation times

A general theory, based on density matrix calculations, has been developed for the special case of a two-pulse sequence applied to spin 1 (¹⁴N) nuclear quadrupole resonance (NQR) of a powder sample. It is shown that the homolog of the NMR inversion-recovery experiment leads easily to the spin-lattice relaxation time T ₁ (associated with the diagonal elements of the density matrix) provided that an appropriate phase cycling is used. Conversely, in spite of two-step phase cycling schemes adapted to spin-spin relaxation measurements, the homolog of the NMR Hahn spin-echo sequence may pose some problems if the results are displayed in the magnitude mode. First, at short decay times, the echo may be corrupted by unwanted signals. Secondly, in that case, the amplitude of the resulting signal can evolve unexpectedly and differently as a function of the phase of the second pulse. Thirdly, at long decay times, the echo maximum occurs earlier than expected. All these problems in principle disappear with a complete four-step phase cycling scheme and the echo decay curve yields reliably the spin-spin relaxation time T ₂ (associated with off-diagonal elements). This theory allowed the exploitation of many test experiments performed at different frequencies on hexamethylenetetramine (HMT) and sodium nitrite.     

14N nuclear quadrupole resonance in several liquid crystals in their solid state

Nitrogen-14 nuclear quadrupole resonance (NQR) spectra in several liquid crystals in their solid state have been detected at 77 K, using a pulsed spectrometer. The quadrupole coupling constants (e²qQ) and asymmetry parameters (η) for the nitrogens have been calculated.     

14N nuclear quadrupole resonance of some sulfa drugs

The 14N nuclear quadrupole double resonance spectra of different polymorphs of sulfanilamide, sulfadiazine, sulfamerazine and sulfamethazine have been measured and the 14N quadrupole coupling tensors have been determined. The obtained 14N spectra are compared with those of other sulfa drugs like sulfathiazole. It is shown that different polymorphs can be easily discriminated. The application of this technique for non-destructive analysis, polymorph determination and quality control in the production of pharmaceuticals is stressed.     

Polarization enhancement technique for nuclear quadrupole resonance detection

We demonstrate a dramatic increase in the signal-to-noise ratio (SNR) of a nuclear quadrupole resonance (NQR) signal by using a polarization enhancement technique. By first applying a static magnetic field to pre-polarize one spin subsystem of a material, and then allowing that net polarization to be transferred to the quadrupole subsystem, we increased the SNR of a sample of ammonium nitrate by one-order of magnitude.     

14N Pulsed nuclear quadrupole resonance. 2. Effect of a single radio-frequency pulse in the general case

A novel theory, based on density operator calculations, is provided for assessing the nuclear quadrupole resonance behaviour of a spin 1 (¹⁴N) subjected to a single radio-frequency pulse. It is for a powder sample in zero magnetic field for an electric field gradient tensor without symmetry. A complete set of equations is obtained for the quantities of interest. It is derived from the general Liouville–von Neumann equation and from a proper basis on which the density operator is expanded. Theoretical results, in terms of signal evolution as a function of the pulse length (nutation experiments), show that the same nutation curve is expected for the three different transitions which exist when the electric field gradient tensor is without symmetry. This latter nutation curve is, however, different from that which prevails in the case of an axially symmetric tensor, this apparent discrepancy being easily resolved on theoretical grounds. Experimental data (for NaNO₂, electric field gradient tensor without symmetry) are checked against values of the radio-frequency field amplitude provided by NMR measurements performed with the same equipment. Good agreement between theory and experiment is obtained.     

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.     

Detection of plastic explosives in luggage with14N nuclear quadrupole resonance spectroscopy

Nuclear quadrupole resonance (NQR) of¹⁴N nuclei has many advantages as a method for detecting nitrogen-containing explosives, the most important are very high chemical specificity, true noninvasive operation and detection of bulk explosive in situ only (no vapor or particular capture needed). One of the most high explosives is hexogen (RDX) often used by terrorists in plasticized forms. The ring nitrogen nuclei in an RDX molecule generate three sets of NQR frequencies corresponding to three physically nonequivalent positions of the molecule in the crystal lattice. The prototype device we have constructed is intended for inspection of suitcases for the presence of plastic explosives containing RDX or octogen by¹⁴N quadrupole resonance. It is essentially a fully automated PC-controlled pulsed FT NQR spectrometer equipped with a large volume (70 1) radio-frequency (RF) sample coil to accommodate a typical suitcase. The device consists of a measure chamber with an RF coil, tuning and matching box, an RF pulse transmitter and a control PC with dedicated cards like digital receiver, frequency synthesizer, pulse programmer and probe-tuning controller. The control software finds the NQR lines and measures their frequencies. An alarm is produced if any of these frequencies matches the characteristic NQR frequency of the explosive and the signal-tonoise ratio exceeds the preset threshold. Multipulse sequences of the type SORC (strong off-resonance comb) or SLSE (spin-locked spin echo) were used in order to increase the allowed data acquisition rate. We could detect 230 g of PMW-8, a plastic explosive (containing 81% of RDX) in 10 s or 100 g in 30 s. Detection probability was not less than 90%.     

Special features of remote observations of weak signals from 14N nuclear quadrupole resonance

The case of excitation of nuclear quadrupole resonance (NQR) in nitrogen-containing compounds is examined for significant sample removal under conditions of strong dispersion of the registered signal. Principal limitations on the sensitivity of remote NQR observations are demonstrated. A method of registering resonant lines after fading of the main signal is suggested. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 8–11, August, 2008.     

Two-frequency method for increasing the signal-to-noise ratio for nuclear quadrupole resonance14N low-frequency transitions

A method is proposed for increasing the signal-to-noise ratio during detection of NQR¹⁴N low-frequency transitions, consisting in a preliminary saturation of the _o(_–) transition before accumulation of the multiplet signals of the spin echo or induction signals, observed during the action of a series of 90 pulses on the _–(_o) transition. The gain in signal-to-noise ratio achieved by the two-frequency action is calculated theoretically, and the maximum value is found to be 3/(3 –) for _– and 3(1 + )/4 for _o. It is shown that the envelope of the induction signal for an increase in the time between the 90 pulses decreases according to one exponent for _o, while for _– and ₊ it decreases according to two exponents, and the approach to equilibrium of the system of¹⁴N nuclei is oscillatory in nature.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 61–64, November, 1987.     

Hydrogen bonds in single crystals of para and meta-aminobenzonitrile as revealed by the Zeeman effect on the nuclear quadrupole resonance of 14N

The |e ² qQ/h| and η values for both the cyano and the amino-nitrogen of the title compounds are reported at room temperature as well as at 273 K and 77 K. From Zeeman effects on single crystals of both compounds the orientation of the principal axes of the electric field gradient (efg) on both nitrogen nuclei, as well as a number of data on the crystallographic and molecular structure, are obtained. A reliable interpretation is given of the experimental resonance frequencies, which are also safely assigned to the right nitrogen atoms. By studying the dependence of the resonance linewidth on the orientation, with respect to the efg principal axes, of the Zeeman field B ₀, the spatial distribution of the hydrogen nuclei around the ¹⁴N nuclei is determined. In this way hydrogen bonds are shown to exist in both single crystals. An analysis based on the Townes and Dailey theory allows an estimate to be made of the possible variation of the population of the cyano-nitrogen lone-pair orbital when involved in hydrogen bonds.     

Measurement of the nuclear quadrupole moment of53Cr by laser-Rf double resonance

The hyperfine structure of the metastable atomic states (3d ⁴4s ²)⁵ D _1,2,3,4 of⁵³Cr has been measured using theABMR-LIRF method (atomic beam magnetic resonance detected by laser induced resonance fluorescence). The dipole coupling constantsA and the quadrupole coupling constantsB are found to beA(⁵ D ₁)=?17.624(2) MHzB(⁵ D ₁)=?21.847(5) MHzA(⁵ D ₂)=?25.113(2) MHzB(⁵ D ₂)=?13.485(5) MHzA(⁵ D ₃)=?35.683(2) MHzB(⁵ D ₃)=15.565(5) MHzA(⁵ D ₄)=?48.755(2) MHzB(⁵ D ₄)=63.021(5) MHz. From these measured hfs constants the electric quadrupole moment for⁵³Cr is calculated to beQ=?0.15 (5) barn. The 30% error takes into account the uncertainties due to configuration interaction effects (shielding and antishielding effects) and of deviations from pure SL-coupling for the states⁵ D _1,2,3,4.     

Emission of nuclear quadrupole resonance from polycrystalline hexamethylenetetramine

The angular dependence of the nuclear quadrupole resonance (NQR) signal intensity emitted from polycrystalline hexamethylenetetramine has been analytically investigated for all directions for non-contact detection of chemicals by nuclear quadrupole resonance. The field pattern of the NQR signal from a column sample was measured. The emitted patterns were the same as that from a united single magnetic dipole, which fitted well to the estimation based on quadrupole principle axis system. This result is helpful to design an antenna for NQR remote detection.     

14N and35Cl nuclear quadrupole double resonance study of the structural phase transitions in N-octylammoniumchloride

The structural phase transitions between the non-intercalated phases of the layer structure compound N-octylammoniumchloride have been studied via proton-¹⁴N and proton-³⁵Cl nuclear quadrupole double resonance. The results have been related to an order-disorder model of the octylammonium chains. The temperature dependence of the order parameters of the –NH₃ head groups has been determined.     

14N and35Cl nuclear quadrupole double resonance study of the phase transitions in n-decylammoniumchloride and n-hexylammoniumchloride

The structural phase transitions between the intercalated and the non-intercalated phases of the layer structure compound n-decylammoniumchloride and n-hexylammoniumchloride have been studied via proton-¹⁴N and proton-³⁵Cl nuclear quadrupole double resonance. The results have been related to an order-disorder model of the alkylammonium chains. The temperature dependence of the order parameters of the –NH₃ head groups has been determined.