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.     

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.     

EPR studies of15N- and2H-substituted pH-sensitive spin probes of imidazoline and imidazolidine types

The isotopically substituted analogs of pH-sensitive imidazoline and imidazolidine radicals have been synthesized and investigated with electron paramagnetic resonance (EPR) spectroscopy. The introduction of²H and¹⁵N into the structure of the radical is a useful approach to enhance the information obtained from spin-labeling experiments. The spectra of the radicals have been analyzed with 9.8 (X-band) and 130 GHz (D-band) EPR spectroscopy. The substitution of¹H for²H leads to significant narrowing of Gaussian line width, while the substitution of¹⁴N for¹⁵N in the nitroxyl fragment decreases both the number of spectral lines and Lorentzian line width. These effects result in a significant increase in the peak intensities up to 5–7 times for X-band EPR spectra of one of the imidazoline radicals (R4). The increase in spectral resolution allowed us to reveal the hyperfine interaction splitting with the attached proton (0.36 G) in the protonated form of the radical R4. The influence of proton exchange of the radicals with phosphate and acetate buffers on their EPR spectra has been studied in H₂O and D₂O. The corresponding rate constants of the proton exchange have been calculated from fitting of the simulated EPR spectra line shapes to experimental spectra. The data obtained demonstrated the advantages of the isotopically substituted spin pH probes in spectral resolution and sensitivity which can be an important factor particularly for applications in vivo where the fundamental sensitivity is much lower. The sensitivity of EPR spectra of these spin probes to the buffer capacity could be of practical importance taking into account the biological relevance of monitoring this parameter in some pathological states.     

Interferometric frequency measurements of 130Te2 transitions at 486 nm

Doppler-free spectra of ¹³⁰Te₂ have been investigated in the region of 486 nm, close to the Balmer-β transitions atomic hydrogen and deuterium. The frequency ratios between a 633 nm He-Ne laser stabilized to the 11-5 R(127) “i” transition in ¹²⁷I₂ and two of these ¹³⁰Te₂ Doppler-free components have been measured interferometrically to a precision of 2 parts in 10¹⁰ (one standard deviation). These measured components constitute useful transfer standards for the measurement of absolute frequencies of both the Balmer-β transitions and the 243-nm two-photon 1S-2S transitions in hydrogen and deuterium.     

Determination of the structure of benzonitrile by nuclear magnetic resonance : Analysis of 1H and 13C spectra of benzonitrile dissolved in isotropic and nematic phase

The ¹H- and ¹³C-N.M.R. spectra in isotropic solution have been obtained for benzonitrile and mono ¹³C benzonitriles. The spectra have been analysed to yield values of chemical shift, H,H and ¹³C,H coupling constants. ¹H N.M.R. spectra of benzonitrile and enriched ¹³C species of benzonitrile have also been obtained in the nematic phase. From the dipole-dipole coupling constants a molecular structure has been deduced and compared to the microwave substitution structure previously known. The sources of deviations between the results from various methods of structural determination are discussed.     

Accumulation of deuterium in radiation-damaged tungsten

Experimental studies have been performed to determine the effect of high-level radiation damage on the accumulation of deuterium and erosion of tungsten samples exposed to deuterium plasma. Tungsten samples were exposed first to fast helium ions having an energy of 3–4 MeV (providing from one to ten displacements per atom) and then to deuterium plasma up to a dose of 10²⁵ ion/m². The effects of deformation and modification of the surface microstructure have been observed. The concentrations of helium and deuterium have been measured by the methods of elastic nuclear proton backscattering and nuclear recoil detection of helium ions. A high concentration of deuterium in the damaged layer of a tungsten sample has been measured, and helium has been detected in a layer ～5 μm thick. The proposed method shows promise for determining the lifetime of materials used in fusion reactors and measuring the concentration of tritium accumulated in these materials.     

Use of the satellites of the 13C and 125Te obtained in the P.M.R. spectra of nematic liquid crystal mesophases

The complete r ^α structure of tellurophene has been determined from proton magnetic resonance spectra, including ¹³C and ¹²⁵Te satellites, obtained in three thermotropic nematic mesophases. The molecular structures observed in the different solvents have been compared both to each other and with microwave data, and discussed with respect to possible solute-solvent interactions. Isotropic P.M.R. spectra and the relative heteronuclear sub-spectra have also been analysed in order to obtain all the J_ij indirect coupling constants. Absolute signs were determined for ² J _TeH and ³ J _TeH. The anisotropic contribution to the Te-H indirect couplings was found to be negligible.     

Structure and symmetry of azulene as determined from microwave spectra of isotopomers

The rotational spectra of six ¹³C isotopomers in natural abundance and of eight synthesized deuterium isotopomers of azulene have been measured using pulsed nozzle cavity and waveguide Fourier transform microwave (FTMW) spectrometers over the 8–18?GHz range. The spectrum of the parent species was remeasured with the higher resolution of FTMW spectrometers. Rotational constants have been fitted to the measured frequencies of the rotational transitions of all measured isotopomers. In addition, centrifugal distortion constants were determined for the parent species and the deuterated isotopomers. The permanent electric dipole moment was redetermined from Stark splittings. The C_2v covering symmetry of the azulene molecule has been demonstrated unambiguously from a single set of observed transitions for the asymmetrically substituted 1-, 4-, 5- and 9-¹³C–isotopomers at twice the intensity of the symmetrically substituted 2- and 6-¹³C–isotopomers. The positions of all nuclei of the planar non–alternating aromatic ring system of azulene have been determined from moments of inertia of all available isotopomers. Different methods have been used to arrive at a near equilibrium structure.     

Measurement of the polarized parton distribution functions at HERMES

The HERMES experiment at DESY has measured the inclusive and semi-inclusive double-spin asymmetries of polarized positrons scattering from polarized hydrogen and deuterium targets in the kinematic range of Bjørken-x 0.023 < x < 0.06 and 1 GeV ² < Q ² < 10 GeV². A RICH detector was installed for the deuterium running period and by providing the identification of charged pions and kaons has enabled the first measurement of charged kaon asymmetries. Based on the measured proton and deuterium asymmetries the polarized quark distributions have been extracted in leading-order pQCD.Received: 30 September 2002, Published online: 22 October 2003PACS: 13.60.Hb Total and inclusive cross-sections (including deep-inelastic processes) - 13.88. + e Polarization in interactions and scatteringJ. Stewart: For the HERMES Collaboration     

The proton N.M.R. spectrum of partially oriented norbornadiene. Molecular structure and the effect of vibrational averaging

The proton N.M.R. spectrum of norbornadiene partially oriented in the nematic solvent, Merck Phase (IV), has been measured and compared with an earlier study using EBBA as solvent. It is shown that the structure of the proton framework is significantly different in the two nematogens. Vibrational averaging of the dipolar couplings is carried out in order that effective r_z structures can be compared.     

Transverse asymmetries at backward angles in G0

The backward angle phase of the G0 experiment has measured the beam-normal single-spin asymmetries in elastic scattering of transversely polarized electrons from the proton and made the first measurement in quasi-elastic scattering in deuterium at backward angles for Q²?=?0.22 GeV²/c² and 0.63 GeV²/c². The measurements were made at a lab scattering angle of 108° at beam energies of 362 MeV and 687 MeV respectively. Preliminary results for the proton are consistent with including ??N states in the calculation of the asymmetry in the resonance region. A preliminary estimate of the beam-normal single-spin asymmetry for the scattering from the neutron is made using a quasi-static deuterium model.     

NMR studies on hydrogen bonding and proton transfer in Mannich bases

A review of studies on the ortho Mannich bases containing various substituents in the phenyl ring on the basis of¹H,¹³C and¹⁵N nuclear magnetic resonance (NMR) spectra in various solvents over the temperature range 110–298 K is presented. Some new results are also included. The data gathered so far show that there is some critical (inversion) range of ΔpK _a (= pK _a(NH⁺) − pK _a(OH)) in which the proton transfer equilibrium appears. This inversion range is well reflected in the behaviour of secondary deuterium isotope effect in¹³C NMR spectra. A strong temperature effect on the strength of hydrogen bonding should be emphasized. The¹H chemical shift for trichloroderivative increases from 13.5 at room temperature up to 17 ppm at 130 K when the proton is equally shared between the bridging atoms (¹ J(¹H,¹⁵N) = 30–40 Hz). The potential for the proton motion in such bridges is discussed taking into account the behaviour in the ultraviolet and infrared spectra. The role of dimerization in proton transfer equilibria is shown. In addition the rotation of OH groups involved in hydrogen bond formation and nitrogen pyramidal inversion was studied by the¹H dynamical NMR spectra.     

Crystal growth and thermal and optical properties of La3Ga5SiO14 single crystals

We have grown an almost colorless La₃Ga₅SiO₁₄ single crystal with a dimension of 26 mm using the Czochralski technique. X-ray powder diffraction of sintered material and the single crystal were performed at room temperature. The thermal expansion coefficients along Y and Z directions have been measured to be 5×10^-6 K^{- 1} and 3.8×10^-6 K^-1, respectively. The specific heat of the crystal has been measured to be 0.90 J/gK at 453.15 K. The transmittance spectra from 200 to 800 nm were measured. PACS 61.10.N; 78.70.E; 65.40.D; 65.60; 78.20.C     

N.M.R. Studies of Lanthanide(III) Complexes. High Field Shifts in Complexes of 1,10-Phenanthroline

In continuation of our studies on the complexes of lanthanide(III) ions with N-donor ligands^1,2, especially those of 1,10-phenanthroline (phen)^3,4, we wish to report the proton N.M.R. spectra of several lanthanide(III) complexes of phen in aqueous (D₂O) solution at 330 K. Table 1 contains the observed chemical shifts of the four types of protons in phen relative to the methyl resonance of the internal standard 2-methyl-2-propanol. For comparison, the spectrum of an authentic sample of Nd(phen)₂Cl₃.2H₂O complex prepared by the method of Sinha⁵ was recorded and the spectrum found to be virtually indistinguishable from that obtained by mixing the individual components in the proper ratio.     

Nitroxide radicals

The proton hyperfine constants have been measured, using N.M.R., for a series of sterically hindered alkyl aryl nitroxides. Computer reconstructions of the electron resonance spectra show that the coupling constants obtained from the pure radical are very similar to those obtained from the electron resonance spectra of dilute solutions. Comparison of methyl and proton splittings in identical positions suggests that the radicals are σ in character although the molecular-orbital calculations are unable to distinguish between σ or π radicals.     

D2O‐catalyzed proton transfer selectivity of 4 different NH protons in the same molecule

When N‐benzyl‐N′‐methylacetamidinium hydrochloride (pKa=11.8) is dissolved in D₂O/DCl(1 M), an equilibrium of 2 54:46 stereoisomers in an ~2:1 =(R)N^δ+H(D) D/H ratio is formed. Therefore, 2 R =N‐benzyl (E and Z) and 2 R =N‐methyl (E and Z) groups attached to the corresponding H(D) (Z and E) for a total of 8 ¹H‐NMR signals are observed. Consequently, their rates of H and D transfer to D₂O can be measured by means of the ¹H‐NMR broadness (line shape) of the =(R )N^δ+H doublets and =(R )N^δ+D broad singlets. Acidity selectivity is observed for both processes. In fact, the relative proton and deuterium transfer rates follow the acidity order: =(PhCH₂)N^δ+‐H(E) > =(PhCH₂)N^δ+‐H(Z) > =(Me)N^δ+‐H(E) > =(Me)N^δ+‐H(Z). Proton transfer rates are in the range of 8 to 0.5 s^‐1 with α = .92. This tendency is independently supported by the observed experimental chemical shift deuterium isotopic perturbation. The rate‐limiting step for proton exchange is the breaking of the hydrogen bond due to the fast amidine reprotonation (~10¹¹ s). =(R)N^δ+D/=(R)N^δ+H equilibration is reached at ~80 s, and it can be measured by the relative =(R) N^δ+H versus =(R) N^δ+D signal integrations. The equilibrium of the 4 =(R)N^δ+H(D) centers is shifted toward deuterium, but they are further shifted in the more basic centers. Equilibrium is completely shifted toward D in the 4 centers when OD^? contributes with the exchange process at pD > 3.     

Un exemple d'utilisation spécifique de la RMN du carbone-13: les transferts protoniques sur centre carbone

A new method is described to study proton transfers on a carbon centre by means of carbon-13 N.M.R., using non-enriched samples, and without proton decoupling. As an example, the proton exchange rate k between dimethylsulphoxide and its conjugate base, the dimsyl ion, is measured at 25°C : k = 22·1 M^-1 s^-1.     

Structural,optical, thermal and mechanical characterization of an organic nonlinear optical material: 4-methyl-3-nitrobenzoic acid single crystal

Organic single crystals of 4-methyl-3-nitrobenzoic acid (4M3N) have been grown by slow evaporation solution growth technique at room temperature. The single crystal X-ray diffraction study reveals that 4M3N crystallizes in monoclinic system with space group P21/n. The crystalline perfection of the crystal was analyzed by high resolution X-ray diffraction (HRXRD) measurements. The functional groups present in 4M3N have been identified from FT-IR and FT-Raman spectra. The lower cut-off wavelength of 4M3N is found to be 404 nm and the optical band gap is calculated as 2.91 eV. The refractive index shows normal behavior with wavelength. The physio chemical changes, decomposition and stability of the 4M3N compound were established by TG-DTA studies. Vickers microhardness measurement concludes that 4M3N belongs to soft material (n=2.5) category. The LDT value is found to be higher than that of KDP and some of the important organic NLO materials. The third order nonlinear refractive index and nonlinear absorption coefficient of the 4M3N have been measured by Z-scan studies. The imaginary and real parts of the third-order susceptibility values were determined as Im χ³=9.129×10⁻¹¹ esu and Re χ³=1.4034×10⁻⁹ esu respectively. The dislocation density was calculated to be 3.0448×10⁶ cm⁻² which indicates the quality of the crystal.     

Proton N.M.R. study of the dynamics of the ammonium ion in ferroelectric langbeinite, (NH4)2Cd2(SO4)3

The proton N.M.R. lineshape of polycrystalline Langbeinite, (NH₄)₂Cd₂(SO₄)₃, has been studied in the temperature range 300 K to 1·8 K. The resonance line is motionally narrowed over the entire temperature range, and the low temperature proton line shows clear evidence for tunnelling motion of the ammonium ion between spin-symmetry states. From a computer simulation of the lineshape, we obtain an estimate for the tunnelling splitting parameter, J, of the torsional ground state of the ammonium ion, as 375 ± 125 gauss. For an undistorted tetrahedral crystal field this corresponds to a tunnelling splitting Δ = 4J = 6·3 ± 2·1 MHz.

Pulsed proton N.M.R. studies have also been carried out on the above compound at 30·8 MHz and 48·2 MHz and the spin-lattice relaxation time (T ₁) has been measured by the π - t - π/2 pulse sequence as a function of temperature down to 77 K. At 30·8 MHz, a T ₁ minimum of 13 ms occurs at 105·8 K, and is ascribed to random reorientations of the NH₄ ⁺ ion. An activational energy barrier of 0·74 ± 0·1 kcal/mole and an associated pre-exponential factor of 8·0 × 10^-13 s are calculated for the above motional process, and the value of the activation energy is correlated with the tunnelling splitting of the torsional ground state.

An anomaly in T ₁ has been observed at the ferroelectric Curie point (95 K), indicating the order-disorder nature of the transition. This is the first experimental evidence relating to the nature of the transition in Langbeinite.     

Definitive Carbon-13 Chemical Shift Assignments in 2-Substituted Adamantane Derivatives by Deuterium Isotope Effects

Deuterium isotope effects on carbon-13 chemical shifts in 5-[²H]-isotopomeres of ten 2-substituted adamantane derivatives were determined and used for complete assignment of their carbon-13 NMR spectra.

The carbon-13 NMR spectra of ten 2-substituted adamantane derivatives have been assignated by consideration of deuterium isotope effects. Some four- and five-bond downfield deuterium effects on certain chemical shifts have been measured and attributed to remote hyperconjugative interactions.