Oxygen isotope effect in high-T C superconductors: Cu nuclear quadrupole resonance relaxation rates

A scaling relationship has been observed between the⁶³Cu(2) spin-lattice relaxation rates 1/T ₁,(18) and 1/T ₁(16) observed in¹⁸O- and¹⁶O-exchanged YBa₂Cu₄O₈ and the normalized temperatureT/T _c(18 or 16). This relation implies thatT _C is decreased by the change in antiferromagnetic (AF) spin fluctuation rate. Thus oxygen isotope effect observed in high-T _C superconductors does not indicate any importance of electron-phonon interaction but it appears to originate from the change in AF fluctuations.     

Anisotropic relaxation and motion of half-integer quadrupole nuclei studied by central transition nuclear magnetic resonance spectroscopy

An efficient theoretical formalism and advanced experimental methods are presented for studying the effects of anisotropic molecular motion and relaxation on solid-state central transition NMR spectra of half-integer quadrupole nuclei. The theoretical formalism is based on density operator algebra and involves the stochastic Liouville–von Neumann equation. In this approach the nuclear spin interactions are represented by the Hamiltonian while the motion is described by a discrete stochastic operator. The nuclear spin interactions fluctuate randomly in the presence of molecular motion. These fluctuations may stimulate the relaxation of the system and are represented by a discrete relaxation operator. This is derived from second-order perturbation theory and involves the spectral densities of the system. Although the relaxation operator is valid only for small time intervals it may be used recursively to obtain the density operator at any time. The spectral densities are allowed to be explicitly time dependent making the approach valid for all motional regimes. The formalism has been applied to simulate partially relaxed central transition ¹⁷O NMR spectra of representative model systems. The results have revealed that partially relaxed central transition lineshapes are defined not only by the nuclear spin interactions but also by anisotropic motion and relaxation. This has formed the basis for the development of central transition spin-echo and inversion-recovery NMR experiments for investigating molecular motion in solids. As an example we have acquired central transition spin-echo and inversion-recovery ¹⁷O NMR spectra of polycrystalline cristobalite (SiO₂) at temperatures both below and above the α–β phase transition. It is found that the oxygen atoms exhibit slow motion in α-cristobalite. This motion has no significant effects on the fully relaxed lineshapes but may be monitored by studying the partially relaxed spectra. The α–β phase transition is characterized by structural and motional changes involving a slight increase in the Si–O–Si bond angle and a substantial increase in the mobility of the oxygen atoms. The increase in the Si–O–Si angle is supported by the results of ¹⁷O and ²⁹Si NMR spectroscopy. The oxygen motion is shown to be orders of magnitude faster in β-cristobalite resulting in much faster relaxation and characteristic lineshapes. The measured oscillation frequencies are consistent with the rigid unit mode model. This shows that solid-state NMR and lattice dynamics simulations agree and may be used in combination to provide more detailed models of solid materials.     

Time-dependence of nuclear magnetic resonance quadrupole interactions for polymers under shear

We consider the problem of performing NMR spectroscopy under conditions of flow, a central issue in Rheo-NMR. By way of example, the effects of rotational motion on the deuterium NMR spectrum are considered for Couette cell experiments involving deformation of polymers under shearing conditions. The polymer was modelled as a power law fluid and for each streamline, the spin Hamiltonian evolved to allow for flow reorientation. The gap-integral spectra are compared with the 'ideal' spectra for a polymer under shear, but without reorientation. It is found that flow does affect the shape of the deuterium spectra, as well as slightly perturbing the splittings.     

Diffusion in nuclear quadrupole resonance

With the aid of the method of random trajectories, formulas have been obtained for the first time for diffusion damping of the amplitudes of nuclear quadrupole spin echo signals because of molecular vibration-rotation in a two-frequency four-pulse program for spin 5/2 and zero asymmetry parameter. The formulas are similar to the result of Hahn for diffusion in NMR.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 14–16, June, 1985.     

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.     

Photon-echo detected nuclear quadrupole resonance spectroscopy

Rare-earth-ion-doped crystals (REICs) have played an important role in quantum information processing due to their excellent coherent properties. In order to obtain the information regarding the hyperfine structures of the rare-earth ions in REICs, optically detected nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) techniques based on RF resonance and various optical detection methods are widely employed in previous works. Here we demonstrate a new method of NQR spectroscopy based on the photon-echo detection. The hyperfine spectra of the ground state (⁷F₀) and the optically-excited state (⁵D₀) of ¹⁵¹Eu³⁺ in Y₂SiO₅ at zero field are obtained. This method can determine the hyperfine splittings within the ground state and the optically-excited state and is shown to be robust against electrical noise. Our results provide an alternative way for optical detection of NMR and NQR with high signal-to-noise ratio.     

The detection of trinitrotoluene by pure nuclear quadrupole resonance

The data of the observation of the nuclear quadrupole resonance signal in trinitrotoluene C₆H₂(NO₂)₃CH₃ are reported. The measurements are carried out on a crude industrial sample of the Chinese manufacturing at 293 K. It is shown that the lines of the monoclinic form and probably orthorhombic forms are present in our spectra, but the most suitable lines for the detection of trinitrotoluene belong to the monoclinic form. The results of our experiments specify an opportunity of application of the pulse method of nuclear quadrupole resonance for the detection of trinitrotoluene in crude industrial samples.     

Two-frequency effects in nuclear quadrupole resonance

A number of new effects which occur in the two-frequency excitation of a multilevel spin-system in nuclear quadrupole resonance are described. Three programs for observing the effect of trapping, used to detect some transitions in a multilevel system in terms of others, for an accurate determination of the asymmetry parameter of the gradient of the electric field, to identify lines of the multiplet spectrum of nuclear quadrupole resonance, and to investigate the phenomenon of cross-relaxation, are proposed. Quantitative estimates are given of the value of the trapping when two neighboring transitions are excited. The phenomenon of slow beats between signals of a two-frequency echo and the frequency of the transition ±3/2±5/2 for = 0 when an external magnetic field is applied is explained. The reason for the short spin-spin relaxation times in the secondary echoes is established. The experimental method and a block diagram of a two-frequency nuclear quadrupole resonance system are described.This paper was presented at an All-Union Symposium on Magnetic Relaxation in June 1971 in Leipzig.Translated from Izvestiya VUZ, Fizika, No. 3, pp. 82–88, March, 1973.In conclusion we wish to thank V. A. Shishkin, M. Z. Yusupov, and A. D. Gordeev, for their help and for useful discussions.     

Some comments on central component nuclear magnetic resonance relaxation rates in ionic conductors

We consider a variety of mechanisms for the NMR relaxation rates of the central component of a quadrupole split line in ionic conductors. These mechanisms suggest an explanation for recently observed frequency independent T₁ minima, associated structure in T₂, and predict some behavior that should and should not be seen in specific types of experiments.     

N nuclear quadrupole resonance in the barbiturates

The ¹⁴N nuclear quadrupole resonance frequencies at 77 K are reported for several barbiturates. Differences between charge densities in the π and various σ orbitals at the nitrogen site are obtained. The charge distributions are correlated with various substituents, and are discussed with emphasis on the effects of phenyl substituents, hydrogen bonding, and formation of the sodium salt.     

Composite pulse trains for nuclear quadrupole resonance

In the present work, a multipulse train comprising {±^0°|2^90°-τ-±^180°|2^90°} and {±^0°|2^90°-τ-±^0°|2^270°} composite pulses is suggested for the observation of nuclear quadrupole resonance (NQR) signals from remote objects. It is shown that these pulse trains provide efficient separation of interference signals in the multipulse train, which allows conditions of NQR signal storage for detecting explosives to be improved. Kaliningrad State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 54–57, September, 1999.     

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.     

Crossed-coil detection of two-photon excited nuclear quadrupole resonance

Applying a recently developed theoretical framework for determining two-photon excitation Hamiltonians using average Hamiltonian theory, we calculate the excitation produced by half-resonant irradiation of the pure quadrupole resonance of a spin-3/2 system. This formalism provides expressions for the single-quantum and double-quantum mutation frequencies as well as the Bloch-Siegert shift. The dependence of the excitation strength on RF field orientation and the appearance of the free-induction signal along an axis perpendicular to the excitation field provide an unmistakable signature of two-photon excitation. We demonstrate single- and double-quantum excitation in an axially symmetric system using 35Cl in a single crystal of potassium chlorate (omega(Q) = 28 MHz) with crossed-coil detection. A rotation plot verifies the orientation dependence of the two-photon excitation, and double-quantum coherences are observed directly with the application of a static external magnetic field.     

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.     

Remote detection of double nuclear quadrupole resonance spectra

Remote detection of the spectra of double nuclear quadrupole resonance of nitrogen-containing compounds is considered. A comparison is made of this technique with the cross-relaxation method.     

Capacitor-based detection of nuclear magnetization: nuclear quadrupole resonance of surfaces

We demonstrate excitation and detection of nuclear magnetization in a nuclear quadrupole resonance (NQR) experiment with a parallel plate capacitor, where the sample is located between the two capacitor plates and not in a coil as usually. While the sensitivity of this capacitor-based detection is found lower compared to an optimal coil-based detection of the same amount of sample, it becomes comparable in the case of very thin samples and even advantageous in the proximity of conducting bodies. This capacitor-based setup may find its application in acquisition of NQR signals from the surface layers on conducting bodies or in a portable tightly integrated nuclear magnetic resonance sensor.