The determination and assignment of a complete 14N quadrupole coupling tensor in liquid solution

¹⁴N line splittings in the spectrum of nitrobenzene (neat liquid) and metadinitrobenzene (dissolved in benzene), induced by an external electric field, have been used to determine the complete ¹⁴N quadrupole coupling tensor of these substances. Assuming that both molecules are rigid and planar, and that the quadrupole coupling tensors at the ¹⁴N nuclei are identical, the principal components in a local reference frame (x′, y′, z′) are (eQ/h)V_x′ x′ = ±0.34 MHz (eQ/h)V_y′_y′= ±1.18 Hz and (eQ/h)V_z′_z′ = ±1.52. The z′-direction is parallel to the CN bond and the y?direction is perpendicular to the plane of the nitrogroup. With these data the asymmetry parameter η = 0.55.     

43Ca NMR study of the doping effects in the high temperature superconductor (La1–xCax)(Ba1.75–xLa0.25+x)Cu3Oy

The ⁴³Ca nuclear magnetic resonance is measured in the normal state of the high temperature superconductor (Ca_xLa_1–x)(Ba_1.75–xLa_0.25+x)Cu₃O_y as a function of temperature. The samples are chosen in order to compare the effect of changing the calcium and the oxygen contents in the underdoped regime. We determine the quadrupolar parameters and the Knight shift (KS). The macroscopic magnetic susceptibility is measured and used to estimate the ⁴³Ca hyperfine field. The variation of KS when increasing the calcium content does not show the signature of an increase of the doping level, contrary to what is suggested by the variation of macroscopic properties.     

Angular dependence of 1H- and 2H-NMR spectra of H2O and D2O absorbed in cellulose acetate film

¹H- and ²H-NMR spectra of H₂O and D₂O absorbed in cellulose acetate films were observed while changing the angle between the plane of the film and the magnetic field. ¹H-NMR spectra show dipolar splittings that vary depending on the angle. The splitting has a maximum when the surface of the film is perpendicular to the magnetic field. From the angular dependence of the dipolar splitting, it is recognized that the proton-proton dipolar axis of water molecules tends to orient perpendicularly to the surface of the film. ²H-NMR spectra that show quadrupolar splittings also indicate that the quadrupolar axis tends to orient perpendicularly to the film. The so-called bound water and free water in the film can exchange rapidly on the NMR time scale, so that the line width and the splitting of the NMR spectra become smaller as the amount of water in the film increases. From the temperature dependence of line widths, the apparent reorientational activation energy of water molecules in the film is estimated to be 25 kJ/mol from ¹H-NMR and 31 kJ/mol from ²H-NMR.     

Nematic conformation of oxyethylene spacers involved in main-chain liquid crystals

²HNMR measurements were performed on main-chain dimer and polymer liquid crystals (LC) having oxyethylene (OE) spacers -(OCH₂CH₂)_xO-(x=2, 3). The orientational as well as conformational characteristics of these molecules have been investigated in bulk and in a nematic solution. The OE spacer was found to take spatial arrangements characteristics of the nematic phase. The nematic conformation of the spacer remains nearly invariant over a wide range of temperature and concentration. In these analyses, the ratio of the deuterium quadrupolar splittings Δν/Δν^R (Δν: spacer and Δν^R: mesogenic unit) provided an important information regarding the spatial configuration of molecules in the LC state. The results obtained in this study are consistent with our previous conclusion drawn on a series of main-chain LC oligomers and polymers comprising n-alkane spacers -O(CH₂)_nO- (n=9, 10).     

Solubility product and related thermodynamic quantities of silver and barium chromates in formamide

The values of ΔG⁰, ΔH⁰, and ΔS⁰ for the dissolution process, M₂(CrO₄)_x + solvent — 2 M^x+ (solvated) + xCrO₄^2? (solvated), where M is Ag or Ba, and x is 1 or 2, have been determined in formamide from solubility studies. The negative value of ΔS⁰ indicates that there is more order in the dissolved state than in the undissolved state.     

The g-value of the 2E state of K3CR(CN)6 and the lower symmetry field

The ⁴A₂ → ²E transition of potassium chromicyanide has been studied under magnetic field. It has been found that the g-value is nearly isotropic, quite unlike the case of ruby. An attempt has been made to explain the zero-field splittings of ^2E, ²T₁ and ²T₂ states and the g-value of the ²E state on the assumption that the distant ions are mainly responsible for lowering of symmetry of the crystal field from O_h. A reasonable choice of parameters can make the calculated values agree with the observed ones.     

Magnetic field-induced ΔF=±2,3,4 transitions in the Eu I-spectrum

The occurrence of ΔF=±2, ±3, and ±4 transitions in the hyperfine structure of the Eu I lineλ 629.1 nm (4f ⁷6s ² a ⁸ S _7/2?4f ⁷6s6p z ⁸ P _5/2) was investigated with the application of high-resolution laser-atomic-beam spectroscopy. It was possible to show that the appearance of such transitions depends on the magnitude of an external magnetic field. Calculations of the hyperfine Zeeman splittings of the excited and the ground state were performed. This allowed the identification of the forbidden transitions.     

Resolution limits in magic-angle rotation NMR spectra of polycrystalline solids

Dependence of linewidth in porton-decoupled ¹³C NMR spectra of diamagnetic polycrystalline samples on external magnetic field strength is studied. Spectral resolution is limited by magnetic heterogencity of powder samples. It is suggested that in magic-angle rotation spectra, the linewidth is determined by the amsotropy of the magnetic susceptibility Δ_xυ rather than _xυ of the crystallites.     

Optical and ODMR investigation of the low lying excited states of neat α-oxalic acid dihydrate

The lowest excited singlet and triplet states of neat α-oxalic acid dihydrate have been investigated by optical, optical Zeeman, and zero-field optically detected magnetic resonance (ODMR) spectroscopy at T ? 4 K. The observed electronic transitions in absorption are assigned as ¹A_u ← ¹A_g (ν₀ = 34131 cm^?1) from its normal polarizatio These correspond to the expected lowest lying ^1,3nπ* excitations in trans-α-dicarbonyls. The ³A_u → ¹A_g phosphorescence is also observed. Monitoring the phosphorescence intensity, the fine structure splittings and principal axes' orientation and the kinetic parameters of the ³A_u s The fine structure constants are X = 2510.0, Y = ?1800.3, and Z = ?709.7 MHZ where the x axis is in-plane and parallel to the carbo The absolute signs of the constants have been established by optical Zeeman measurements. The τ_x zero-field spin state has the largest total phosphorescence rate, radiative rate, and populating rate. The τ_x activity in the 0 - 0 band is polarized mainly along the x axis. However, considerable normal polarization associated with an in-p     

Nuclear magnetic relaxation of ionic nuclei moving in an external electric field

We have experimentally investigated nuclear magnetic relaxation of some quadrupolar ionic nuclei (²³Na⁺, ⁸⁷Rb⁺ and ³⁵Cl⁻ ) in electrolyte solutions in non-equilibrium states. The measurements of relaxation rates 1/T₁ in the presence of a direct electric field, and thus also an electric current, revealed that differences can occur in comparison with relaxation in the absence of the field. In some systems no change in the relaxation rate was observed, but in certain other (non-aqueous) systems there was a change in the quadrupolar relaxation rate in the presence of the field.     

A study of the solid solutions (EuO)1−x(LnN)x (where Ln = Nd,Eu, Gd) by europium-151 Mössbauer spectroscopy

The magnitude of the magnetic hyperfine field at Eu^II in the cubic solid solutions (EuO)_1?x(LnN)_x (where Ln = Nd, Eu, Gd) has been determined at 4.2°K by ¹⁵¹Eu Mössbauer spectroscopy. The resultant effective hyperfine field is found to be almost independent of composition because of a number of compensating effects.     

Li ion dynamics in Li3xLa2/3–x□1/3–2xTiO3 studied by NMR

⁷Li nuclear magnetic resonance relaxation times, T₁ and T_1ρ, versus temperature are reported in the 150–900 K temperature range on the lithium lanthanum titanates, Li_3xLa_2/3–x□_1/3–2xTiO₃, which are fast ionic conductors. Two characteristic frequencies of Li⁺ motions are evidenced in these compounds: the first is in the range of the Larmor frequency when the second one is in the range of the radio-frequency field. These frequencies are respectively attributed to motion of the Li⁺ ion inside the cage formed by the oxygen ions and to jumps between the cages. The T₁ and T_1ρ studies on ⁶Li nuclei confirm the above results and show that the relaxation is not due to quadrupolar interaction at a variance, which is generally accepted.     

Nuclear quadrupole coupling constants of thionyl chloride

The nuclear quadrupole structure of some low J transitions with large splittings has been measured for thionyl chloride (SO³⁵Cl₂) and analysed in terms of a first order perturbation. The following nuclear quadrupole coupling constants were obtained: x_aa = ?25.01 ± 0.07 MHz, x_bb = ?0.03 ± 0.45 MHz and x_cc = 25.04 ± 0.45 MHz.     

Effect of the Magnetic Field on the Supramolecular Structure of Chiral Smectic C Phases: 2H NMR Studies

We present a theoretical and experimental ²H NMR study of the effect of external magnetic fields on the supramolecular organization of chiral smectic liquid‐crystalline mesophases, such as SmC* and re‐entrant SmC*. Three experimental cases in which the supramolecular helical structure of the smectic C* phase is unwound by a magnetic field (H), parallel to the helical axes of this phase, are discussed in detail. Unwinding of the helical structure is described by using a theoretical model based on the Landau‐de Gennes theory, which allows us to explain the transition temperatures among the SmA, SmC*, and uSmC* phases. The energy‐density behavior in the vicinity of the transitions and the value of the critical magnetic field H_C for unwinding the helical structure are discussed by applying this model to three ferroelectric smectogens ( MBHB , 11EB1M7 , ZLL7/* ), which are studied by ²H NMR spectroscopy at different magnetic fields (from 2.4 to 9.4 Tesla). Furthermore, the tilt angle of the three smectogens in the SmC* phase has been directly evaluated, for the first time, by comparing the quadrupolar splittings at different magnetic fields. In one case, ²H NMR angular measurements are used to obtain the tilt angle in the re‐entrant smectic C phase.     

Sc Solid State NMR studies of the silicides ScTSi (T=Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt)

The silicides ScTSi (T=Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt) were synthesized by arc-melting and characterized by X-ray powder diffraction. The structures of ScCoSi, ScRuSi, ScPdSi, and ScIrSi were refined from single crystal diffractometer data. These silicides crystallize with the TiNiSi type, space group Pnma. No systematic influences of the ⁴⁵Sc isotropic magnetic shift and nuclear electric quadrupolar coupling parameters on various structural distortion parameters calculated from the crystal structure data can be detected. ⁴⁵Sc MAS-NMR data suggest systematic trends in the local electronic structure probed by the scandium atoms: both the electric field gradients and the isotropic magnetic shifts relative to a 0.2 M aqueous Sc(NO₃)₃ solution decrease with increasing valence electron concentration and within each T group the isotropic magnetic shift decreases monotonically with increasing atomic number. The ⁴⁵Sc nuclear electric quadrupolar coupling constants are generally well reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code.     

Lattice enthalpies and magnetic loops in lanthanide iron garnets,Ln3Fe5O12

Experimental lattice enthalpies Δ_LH^θ of lanthanide iron garnets Ln₃Fe₅O₁₂ (LnIGs) with Ln = Ce − Lu, have been determined from the Born–Haber thermochemical cycle. The results have been compared with those reported by other authors using numerical simulation or an empirical equation. The lattice enthalpy of PmIG has been predicted by linear interpolation between Δ_LH^θ of the adjacent NdIG and SmIG. It has been found that the partial derivative (∂Δ_LH^θ/∂V_m) for the series of LnIGs corresponds by magnitude and dimension to an upper limit of their rigidity. New effect of magnetic loops has been noted in the same series in the dependence of the lattice magnetic entropies on the effective magnetic moments (theoretical and experimental values).     

Molecular zeeman effect in NH3

High-resolution measurements of ΔM_j = 0 inversion transitions in ¹⁴NH₃ in 100 kG magnetic fields were made using a beam-maser spectrometer. The spectra show resolved splittings due to a different in molecular g-values for upper and lower inversion states with J = 3, K = 2. The observed difference in upper and lower inversion state g-values is g⁺(3,2)—g^?(3,2) = (1.38 ± 0.08) > 62;x 10^?4.     

Fluctuation in occupancy of Cu2+ ions in Zn- and Cd-substituted Cu-ferrites

Mössbauer effect technique has been used for the comparative study of Cu_1?x Zn _x Fe₂O₄ and Cu_1?x Cd _x Fe₂O₄ ( _x = 0.0?1.0) ferrites. Both Zn²⁺ and Cd²⁺ cations are divalent, non-magnetic ions with different ionic radii. With the substitution of these non-magnetic cations the average internal magnetic field decreases and paramagnetic behavior is dominated at x = 0.7 in both series. It is observed that the occupancy of Cu²⁺ ions for tetrahedral site is not constant for all compositions but fluctuate between 8–15%. It is also found that Cu²⁺ ions have more preference for tetrahedral site in Cu-Zn system as compared to the Cu-Cd system. Zn²⁺ and Cd²⁺ both ions occupy tetrahedral site completely and form normal spinels for x = 1.0.     

A study of the new perovskite solid solution series SrFexRu1−xO3−y by ruthenium-99 and iron-57 Mössbauer spectroscopy

The magnetic and structural properties of the solid solution SrFe_xRu_1?xO_3?y (0 ? x ? 0.5) have been studied using ⁵⁷Fe and ⁹⁹Ru Mössbauer spectroscopy and other techniques. These phases, which are here reported for the first time, have a distorted perovskite structure. The iron substitutes exclusively as Fe³⁺ and thereby causes oxygen deficiency, but has little effect on the magnetic behaviour of the Ru⁴⁺ until x > 0.2, whereupon the metallic band system begins to revert to a localized electron structure. The properties of a sample with x = 0.3 are complex and intermediate in character. For x > 0.3 the oxygen deficiency is reduced by substantial oxidation to Ru⁵⁺ until at x = 0.5 the system corresponds to Sr₂Fe³⁺Ru⁵⁺O₆.     

Structural analysis of boron compounds using 11B-3QMAS solid state NMR

The structural analysis of three boron compounds, boron carbide (B₄C), silicon tetraboride (SiB₄) and hexagonal-boron nitride (h-BN), were performed using 2D ¹¹B-triple quantum MAS (3QMAS) solid state NMR capable of averaging the second-order quadrupolar interaction of ¹¹B that cause line broadening, splitting and low frequency shift of the central transition (−1/2, 1/2). The coordination number around the boron atom and structural symmetry of each boron compound is discussed by means of the isotropic chemical shift Δσ and the quadrupolar coupling constant C_Q calculated from 3QMAS spectra. Δσ of SiB₄ is quite larger than that of B₄C, which is thought to be caused by its structural distortion and distribution. Δσ of h-BN was found to be higher frequency shift obviously than that of B₄C and SiB₄ because of the difference of the boron coordination number, three-coordinated in h-BN and six-coordinated in B₄C and SiB₄. h-BN has very large C_Q compared to other two boron compounds since the h-BN forming a two-dimensional network has less structural symmetry than B₄C and SiB₄.