19F double resonance in the presence of chemical exchange

The ¹⁹F N.M.R. spectra of CF₂BrCClBr₂ in CS₂ from 20°c to -80°c are reported. Computer-fitting of the experimental spectra using the density matrix formalism of Alexander yields the chemical exchange correlation times and produces a computed internal rotation barrier for trans →gauche of 39·7 ± 0·5 kJ mol^-1 (9·5±0·1 kcal/mole). Results of double resonance studies on the -80°c spectrum upon irradiation of the various peaks with a strong r.f. field are presented. The density matrix equations in the presence of chemical exchange and several relaxation mechanisms were solved to obtain theoretical changes in peak intensities on irradiation. The indirect spin saturation data and their relation to the rate of internal rotation and the relaxation mechanism are discussed. Random field relaxation is shown to be the important relaxation mechanism in the system. The strong irradiation of one component of a strongly coupled spin multiplet with intramolecular exchange causes indirect saturation of the transitions connecting energy levels that have the same m _I values as the one being irradiated whereas the intensities of other transitions are only slightly affected. It appears therefore to be an important complement to the spin-tickling technique in determining energy level diagrams and relative signs of coupling constants.     

Electron paramagnetic resonance and electron nuclear double resonance of the AsO4 4- centre in X-irradiated KH2AsO4

Electron paramagnetic resonance studies of the AsO₄ ^4- centre in X-irradiated crystals of KH₂AsO₄ in the ferroelectric phase at 77 and 4·2 K are reported. The symmetry of the spin-hamiltonian has been found to be orthorhombic, and the g tensor and the A tensor describing the interaction of the unpaired electron with the arsenic nucleus (I = 3/2) have been obtained. Domain splitting has been observed in he spectra recorded in the ab plane of the crystal. By studying these spectra in the presence of an applied electric field, it has been possible to plot the hysteresis curve of ferroelectric KH₂AsO₄. Electron-nuclear double resonance (ENDOR) of protons surrounding the AsO₄ ^4- units has been studied at 4·2 K. Two sets of ENDOR lines have been found arising from the protons in the two equilibrium positions (labelled ‘ close ’ and ‘ far ’) along the hydrogen bonds linking the AsO₄ tetrahedra. The angular variation of the ENDOR lines from both ‘ close ’ and ‘ far ’ protons has been plotted in the crystal symmetry planes. The observed ENDOR frequencies have been fitted to those calculated from the numerical diagonalization of the Hamiltonian. The superhyperfine parameters for the ‘ close ’ and ‘ far ’ protons thus obtained are found to be quite anisotropic. The ENDOR results are shown to explain all details of the partially-resolved proton superhyperfine structure at room temperature as well as at low temperatures. An isotropic contact hyperfine coupling of -2·875 MHz of the unpaired electron to the proton in the ‘ far ’ position of the hydrogen bond has been determined, providing direct evidence for covalency in the hydrogen bonding in KH₂AsO₄ crystals.     

1H NMR relaxation investigation of herbicides interacting with photosystem II preparations fromSpinacia oleracea L.

The interaction of three common herbicides, paraquat, acifluorfen and alachlor, with spinach chloroplast photosystem II (PS II) was investigated by measuring¹H nuclear magnetic resonance spin-lattice relaxation rates, transient nuclear Overhauser effect (NOE) and NOE spectroscopy (NOESY) spectra. Binding to PS II was detected by (i) the enhancement of single-selective relaxation rates and (ii) the decrease in the optimal mixing time providing maximal cross-peak intensity in NOESY spectra. Titration of relaxation enhancements was used to calculate the dissociation constants (K _d) from the bound state for paraquat (K _d = 292 ± 71 μM⁻¹) and acifluorfen (K _d = 311 ± 58 μM⁻¹). A similarK _d was apparent for alachlor. Double-selective relaxation rates allowed the isolation of dipolar relaxation terms between selected proton pairs wherefrom dynamic features of the bound state were evaluated. In all cases the motional correlation time of bound herbicide (τ_c = 0.1−0.4 ns at 300 K) was found two orders of magnitude slower than in the free-solution state. In the case of alachlor the E and Z isomers were observed to bind differently to PS II and a change in conformation could be hypothesized.     

Metal-insulator transition in Bi-doped,amorphous Ga:Ar mixtures: Influence of spin-orbit scattering

Doping amorphous Ga_xAr_1?x mixtures with the strong spin-orbit scatterer Bi has a dramatic effect on the metal-insulator transition (MIT) occurring in this system at a critical metal atomic concentration x_c: (i) the MIT is shifted from x′_c = 0.36 ± 0.01 (corresponding to a critical metal volume fraction v′_c = 0.19 ± 0.01) of the undoped system to a lower value of x_c = 0.25 ± 0.01 (v_c = 0.14 ± 0.01) for (Ga_0.9Bi_0.1)_xAr_1?x and (ii) the critical exponent v and g of the dc conductivity and Hall coefficient, respectively, change from v′ = 0.5 ± 0.1 and g′ = 0 for the undoped samples to v = 1.3 ± 0.3 and g = 0.5 ± 0.1 for (Ga_0.9Bi_0.1)_xAr_1?x.     

Acoustic NMR in spin-1 systems

Acoustic magnetic resonance, both pulsed and continuous has been discussed in terms of the Bloch-Wangsness-Redfield formulation of the magnetic resonance phenomenon. The quadrupolar mechanism has been taken for the spin-phonon coupling and the mutual interaction has been treated in the ‘effective field approximation’. The expressions for the power absorbed both for Δm=±1 and Δm=±2 have been obtained. It is found that from the measurements of the relaxation parameters for Δm=±1 and Δm=±2 it is possible to estimate the non-secular contributions to the line-width. The power absorbed in pulse excitation comes out to be small for short pulse (short compared to the relaxation parameter) and it reduces to the value obtained in continuous excitation for a long pulse. It is seen that for a given pulse-width the signal decreases with the increase of the relaxation parameter and this happens as temperature is lowered. The saturation of electromagnetic signal in presence of the acoustic excitation has also been studied. The analysis indicates that the relaxation parameter obtained from the plot of the relative signal (〈〉_ω/〈〉₀) vs the acoustic frequency ω, is always less than its true value which can be determined by observing the frequency dependence of the relative fractional signal defined as [(〈〉₀?〈〉_ω)/〈〉_ω]/[(〈〉₀?〈〉_2ω0)/〈〉_2ω0].     

Magnetoelastic waves in an in-plane magnetized ferromagnetic plate

The spectrum of magnetoelastic waves propagating along the magnetic field in an in-plane magnetized ferromagnetic plate is numerically investigated in the exchangeless approximation. No restrictions are imposed either on the field pattern of backward volume magnetostatic waves (BVMSWs) or elastic waves supported by a plate of a given geometry across the plate or on the relationship between the sound velocity v _S and the phase velocity of the magnetoelastic waves v=ω/q (ω is the frequency, q is the wave number). The resonance interaction of the BVMSWs and elastic waves is accompanied, as a rule, by the formation of “stop” bands δω that are proportional to the magnetoelastic coupling constant b. When the BVMSWs are in resonance with Lamb and shear elastic modes the values of the magnetoelastic gaps δω at v≈v _S turn out to be of the same order. For v≫v _S , the efficiency of the interaction between the BVMSWs and transverse Lamb modes is almost one order of magnitude higher. If the frequency spacing Δω between the elastic modes is smaller than the mag-netoelastic gap in the spectrum (Δω≤δω), which takes place, particularly, in the region of crowding the elastic mode spectrum (v≈v _S), the resonant interaction results in mixing the dispersion laws for the elastic modes. Namely, a surface mode may transform into a volume one and a shear mode, into the Lamb mode or into a shear mode with another number. The resonance interaction of the shear and Lamb elastic modes not only forms the magnetoelastic gaps δω∼b ² but also changes the efficiency of elastic wave coupling with the magnetic subsystem. This may show up as the coexistence of the effects of “repulsing” both the dispersion laws and the damping decrements of the elastic waves at the resonance frequency. It is shown that magnetostriction splits the cutoff frequencies of both transverse Lamb modes and shear modes, as well as the long-wave (q → 0) frequency limits f ₀ of the BVMSW modes. This may cause the resonance interaction between BVMSW modes of equal evenness in a narrow frequency band Δ∼b near f ₀.     

Low temperature photoconductivity in electron - irradiated p-type Si

The photoconductivity spectra of p-type silicon irradiated at ～15 °K with 1.2 MeV electrons were studied in the wavelength range from 1.2 to 5.5 μ at temperatures from 23 to 80 °K. The 3.9 μ photoconductivity band appears immediately after irradiation in all crystals already at low temperatures, giving further evidence that it is due to the divacancy formed directly during irradiation by electrons. Three main annealing stages of the photoconductivity have been observed; (a) below 160 °K, (b) 160–250 °K, and (c) 280–360 °K. A radiation-induced deep level at E_v , +(0.12±0.02 eV disappears upon annealing at stage b. The annealing behavior of the spectra depends strongly on the measuring temperature. The dependence of the spectra on chopper speed was also investigated.     

Dispersion characteristics for low-frequency magnetoelectric coefficients in bulk ferrite-piezoelectric composites

Ferrite-piezoelectric composites are magnetoelectric (ME) due to the interaction between magnetic and electrical subsystems through mechanical forces. A theory for the low-frequency Maxwell-Wagner relaxation in ME coefficients is discussed for bulk composites of nickel or cobalt ferrite and lead zirconate titanate (PZT). ME coefficients versus frequency spectra show two types of relaxation, over 0.1-100 μHz and 1-1000 Hz. The relaxation frequencies and the magnitude of the ME coefficients are dependent on the electrical and composite parameters and volume fraction for the two phases. The ME coefficient α_E is in the range 10⁻¹-10⁴ mV/cm Oe, higher in cobalt ferrite-PZT than for nickel ferrite-PZT, and is strongly dependent on PZT volume fraction v. Estimates of α_E and relaxation frequencies versus v provided here are useful for engineering composites with maximum ME effects for specific frequency bands.     

Dielectric relaxation,ac and dc conductivities in the fullerenes C60 and C70

The complex conductivity in polycrystalline C₆₀ and C₇₀ has been investigated for frequencies 20 Hz≤ν≤10⁶ Hz and temperatures 10 K≤T≤750 K. The high-frequency dielectric constants ε_α= 2.6±0.1(C₆₀) and ε_∞= 4.6±0.1 (C₇₀) were deduced from these experiments. The observed low temperature relaxation process in C₆₀ fits well into the relaxation dynamics of the C₆₀ molecules as determined by many other experimental techniques operating on very different time scales. In addition to the study of the dipolar relaxation process, the dc and ac conductivities were determined. From the temperature dependence of the dc conductivities energy barriers of E_G=1.75±0.1 eV (C₆₀) and E_G=1.7±0.1 eV (C₇₀) were estimated. In C₇₀ we found indications for small polaron tunneling.     

High resolution FTIR spectra of AsD3 in the 20-1000 cm−1 region. The ground, 98, v2 = 1 and v4 = 1 states

The pure rotational spectrum of the near-spherical oblate symmetric top AsD₃ has been recorded in the 20–120cm^?′ region with a resolution of 2.3 × 10^?3 m^?1 employing an FT interferometer. Rotational transitions with 5 ? J ? 29 and 0 ? X ? 25 of the ground state (GS) and the v₂ = 1 and v₄ = 1 excited states have been assigned. Splittings were observed for the GS, 98, K = 3 and 6 levels, the K = 3 levels of v₂ and the kl = ?2, 1, 4 and 7 levels of v₄. Furthermore the x,y Coriolis coupled v₂ and v₄ bands, v ⁰ ₂ = 654.4149cm^?1, and v ⁰ ₄ = 714.3399 cm^?1, have been examined with a resolution of 2.4 × 10^?3 cm^?1, and ca. 2500 allowed and 336 ‘forbidden’ lines with J′_max = 31 and K′_max = 28 have been assigned. Appropriately weighted GS data comprising FIR lines, allowed and ‘forbidden’ (up to ΔK = ±6) GS combination differences, mmw data, and ΔJ = 0, ΔK = ±1 distortion moment transitions were fitted together, and GS parameters complete through H parameters have been determined. Two different reductions of the Hamiltonian, either with ΔK = ±6 (h₃) or ΔK = ±3 (ε) off-diagonal elements, have been employed. Equivalence of these reductions up to J = 22 was established while for J > 22 the ε reduction is superior. The v₂ and v₄ data have been fitted with two equivalent models based on different reductions of the rovibrational Hamiltonian. In addition to the dominating x,y Coriolis resonance, ζ ^y ₂₄ 0.520, Δ(k ? l) = ±3 and ±6 interactions are important and were accounted for by the models. The transition moment ratio |M₄: M₂| =0.75 has been determined, with a positive sign of the product M ₂ζ ^y ₂₄ M ₄. An improved r₀ structure, r₀(AsD) = 1.51753 Å and α₀(DAsD) = 92.000°, has been determined.     

Microwave spectrum of torsionally excited acetic acid

The microwave spectrum corresponding to the first excited state of the methyl torsion in acetic acid has been identified by means of microwave-microwave double resonance. Although the A-E splittings are extremely large, a reasonable fit has been obtained for the v = 0 and v = 1 states simultaneously by using a Hamiltonian which allows for geometry relaxation upon internal rotation. Barrier parameters are V₃ = 169.90 ± 0.06 cm^?1 and V₆ = ?6.74 ± 0.02 cm^?1. An interpretation of the parameters describing nonrigidity is given in terms of a model with two relaxing bond angles, which is qualitatively supported by ab initio calculations.     

2H-NMR Study of ammonium ion rotational tunneling and reorientation in (ND4)2SnCl6 single crystal

Because of the quadrupole interaction, the²H-NMR spectra of a tunneling ND ₄ ⁺ ion depend on the Larmor frequencyv ₀ and the tunneling frequencyv _t , when both frequencies are less than 20 MHz. Calculated single crystal spectra visualize features to be expected. Significant broadening and asymmetry are observed at level crossing regions aroundv _t =v ₀ orv _t =2v ₀. Angular, frequency and temperature dependences of the spectra are studied using an (ND₄)₂SnCl₆ single crystal. Experimental spectra obtained for different frequencies at 4.2K are fitted withv _t as a parameter. The tunneling frequency is also checked by measurements of the deuteron spin-lattice relaxation timeT ₁ as a fuction ofv ₀. Both methods give consistentlyv _t =7.15±0.10 MHz.     

14N Study of Aromatic Nitroso Compounds

The ¹⁴N NQR frequencies of selected aromatic C-nitroso compounds were measured using cross relaxation double resonance. The monomers have high ¹⁴N NQR frequencies with Χ and η values of 5700 to 6100 kHz and 0.5 ± 0.1, respectively. The dimers and polymer show lower frequencies with values of 2300 to 2600 kHz and 0.8 ± 0.05. Benzofuroxan has values typical of both the monomer and dimer.     

N.M.R. studies of isotopically substituted molecules: The sign of the C≡N coupling constant

A careful study is made of the heteronuclear double resonance of ¹⁴NH₄ ⁺ at modest radiofrequency field strengths corresponding to ‘tickling’. Agreement with theory is obtained and special features of the spin 1 case are pointed out.     

Bandbreite im Threshold-Bereich des 0.63 μ He/Ne-Lasers

A double laser device of high stability was used to determinate the threshold bandwidth of a He/Ne-laser amplifier and oscillator. I. Using one laser as a single-mode oscillator, the other as an amplifier, resonance curves of the amplifier with bandwidths between_IΔv=2.5 · 10³ and 1.7 · 10⁶ Hz were recorded. II. Operating the two lasers as single-mode oscillators, beat frequencies with a bandwidth_IIΔv?100 Hz were observed. Extrapolating these results to the threshold noise power the threshold-bandwidths_IΔv _R ^* =1.4 · 10³ Hz and_IIΔv _R ^* =2.0 · 10³ Hz, respectively, are obtained.     

Thermal depolarisation current study of electron irradiated fluorinated ethylene propylene

Thermally stimulated current (TSC) studies have been reported in the co-polymer of tetrafluoro ethylene and hexafluoropropylene films. Depolarisation current peaks are obtained atα ₁,α ₂ andβ relaxation temperatures of the polymer and the detrapping process is explained on the basis of its molecular motion. A cross-over electron energy of 18 keV is observed where the nature of TSC spectra undergoes a remarkable change. This is explained in relation to the surface states in FEP. Five groups of trapping levels, 0.25±0.08, 0.57±0.10, 1.07±0.1, 1.3±0.25 and 2.3±0.4 eV are obtained.     

Nuclear spin relaxation and magnetic shielding tensors of atoms constituting cyanogen bromide molecule

The temperature dependence of the correlation time describing reorientation kinetics of cyanogen bromide in CDCl₃ solution has been determined on the basis of the linewidths of the ¹⁴N NMR signal. It has been found that the longitudinal spin relaxation of the ¹⁵N nucleus occurs by shielding anisotropy and spin-rotation mechanisms, whereas for the ¹³C nucleus these mechanisms are of lesser importance. In the latter case the scalar relaxation of the second kind due to carbon-bromine coupling is the predominant relaxation mechanism. The parameter values: ¹ J(¹³C—⁷⁹Br) = 349 ± 10 Hz, T ₁ (⁷⁹Br, 303 K) = 2.31 ± 0.22 × 10^?7 s, Δσ(¹⁵N) = 565 ± 16 ppm and Δσ(¹³C) = 276 ± 120 ppm have been determined from the relaxation data analysis. The shielding anisotropy parameters Δσ(¹⁵N) = 580 ± 50 ppm and Δσ(¹³C) = 274 ± 9 ppm have been independently determined using ¹³C and ¹⁵N NMR in liquid crystalline solvent. The experimentally determined shielding tensors for sp-hybridized atoms in the investigated compound and in a series of bromoacetylenes have been compared with the results of quantum mechanical calculations [GIAO, DFT B3LYP/6-311 + +G(2d,p)]. The ‘heavy atom effect’ shielding bromine-bonded carbons is of the order of — 25 ppm and concerns mainly the σ⊥ component.     

Relationship between the parting limit for de-alloying and a particular geometric high-density site percolation threshold

The parting limit or de-alloying threshold for electrolytic dissolution of the more reactive component from a homogeneous fcc binary alloy is usually between 50 and 60 at%. The system that has been most studied, dissolution of Ag from Ag–Au, shows a parting limit close to 55 at% Ag. Here, Kinetic Monte Carlo (KMC) simulations of ‘Ag–Au’ alloys and geometric percolation modeling are used to study the relationship between this parting limit and the high-density site percolation thresholds p _c(m) for an fcc lattice, subject to the rule that atoms with coordination greater than nine are prevented from dissolution. The value of p _c(9) is calculated from geometric considerations to be 59.97 ± 0.03%. In comparison, using KMC simulations with no surface diffusion and no dissolution allowed for ‘Ag’ atoms with more than nine total neighbors, the parting limit is found to be slightly lower (58.4 ± 0.1%). This slight discrepancy is explained by consideration of the local atomic configurations of ‘Ag’ atoms – a few of these configurations satisfy the percolation requirement but do not sustain de-alloying, while a larger number show the converse behavior. There is still, however, an underlying relationship between the parting limit and the percolation threshold, because being at p _c(9) guarantees a percolation path in which successive ‘Ag’ atoms share at least one other ‘Ag’ neighbor. With realistic kinetics of surface diffusion for ‘Au’, the parting limit drops to 54.7 ± 0.3% because a few otherwise inaccessible dissolution paths are opened up by surface diffusion of ‘Au’.     

Determination of the positions of impurity centers in a dislocation core in a NaCl crystal from magnetoplasticity spectra

The spectra of the mean free paths l(ν) of edge dislocations have been studied in NaCl crystals exposed in the electron paramagnetic resonance scheme to the crossed magnetic fields: the Earth’s field (50 μT) and the pump field (2.5 μT, 5–440 kHz). The spectra have been measured for a series of angles θ = 0°–5° of rotation of the sample around its edge [100] with respect to the Earth’s field. The fine structure of the spectra contains a series of peaks whose resonance frequencies are described by the empirical expression v _i ^± = Asin(θ ± Δθ _i ) ≈ A(θ ± Δθ _i ). The parameters Δθ _i are independent of the angle θ within the experimental errors. Within the model of “frozen” magnetic moments associated with impurity center Ca⁺-Cl⁰, the angles Δθ _i characterize the deviation of the axis of the center from the 〈100〉 direction in the core of a dislocation. These angles can be expressed in terms of the spectra obtained: Δθ _i = (? _i ⁺ ? v _i ^? )/2A. The computer simulation of the edge dislocation core provides the set of the angles Δθ _i close to the measured values. The spin-lattice relaxation time of the center on dislocation has been estimated from the low-frequency edge of the spectrum l(ν) as τ _{s ? l} ～ 10^?4 s.     

Nuclear magnetic resonance in ferromagnetic HCP and FCC 59cobalt

The ⁵⁹Co nuclear magnetic resonance spectra of powdered metal have been investigated in the temperature range from 3 K – 295 K. Both HCP resonance lines, coming from nuclei at the center and the edge of the domain walls (v₁ = 221 MHzv₂ = 214 MHz at 295 K, respectively) have been observed as in bulk material. The quadrupole splitting, directly measured only by Kawakami et al., was verified. The line spacing v_q = 3e²Qq/2I(2I - 1)h is v_q = (178 ± 5) kHz at 295 K. A new line with v = 221.7 MHz at 295 K was found, which is probably due to a stacking fault.The temperature behaviour of the FCC-linewidth is anomalous. Between 3 and 10 K a line splitting due to frequency pulling, already predicted by De Gennes et al. in 1962, was discovered. The frequency shift derived from the splitting of the FCC line at 3 K is δω₀ ≈ 2.51 MHz. The corresponding anisotropy field and zero field ferromagnetic resonance frequency of FCC cobalt are H_A ≈ 1.25 × 10² Oe and ω_e ≈ 2.27 × 10⁹ Hz, respectively.