Phase Transitions of Ruthenium-Doped Iron Oxide Studied by 57Fe Mössbauer Spectroscopy at Elevated Temperatures

Hyperfine Interactions - The 57Fe Mössbauer spectra recorded in situ from 5% ruthenium-doped maghemite show parameters typical for maghemite up to 600 K and a hyperfine field distribution...     

High temperature stability of maghemite in partially oxidized basalt lava

Mössbauer spectroscopy of basalt lava samples, exhibiting reversible thermal magnetization (J_S-T) curves with Curie temperatures of about 580°C, has revealed considerable amounts of maghemite (γ-Fe₂O₃) in many samples. In view of the expected instability, of maghemite at temperatures above 350°C, this reversibility is rather surprising. Here we report Mössbauer studies on heated lava samples, showing high content of maghemite. The samples were kept at 600°C in oxidizing, reducing, and inactive atmospheres, respectively, for different lengths of time, and then analyzed with Mössbauer spectroscopy at room temperature. The Mössbauer spectra showed that maghemite is stable in the oxidizing atmosphere for at least several hours. In the inactive atmosphere a considerable amount of maghemite still exists after two hours heating. In the reducing atmosphere maghemite had transformed to magnetite after only 30 minutes.     

Rates of redox reactions in basaltic melts determined by Mössbauer spectroscopy

Mössbauer spectroscopy has been widely used for determining the ferric/ferrous ratio in amorphous rock samples to reveal the oxygen pressure in the melt. In the present investigation, Mössbauer spectroscopy in conjunction with melting experiments at controlled oxygen pressures was used to determine the rates of redox reactions in basaltic melts at 1300°C. The samples were kept at a fixed oxygen pressure long enough to reach equilibrium at a well established ferric/ferrous ratio. Then, the oxygen fugacity in the furnace was changed abruptly and the samples were kept for different lengths of time, from 15 min, to 4 hrs, at the new condition. At the end of each run the samples were quenched and the ferric/ferrous ratio analyzed by Mössbauer spectroscopy. A geological corollary of our results is that natural volcanic glasses, representing quenched melts, retain and reflect the oxidation state in the melt immediately prior to eruption, and hence the oxygen fugacity in the magma.     

Experimental and molecular modeling investigation of (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide

The Schiff base compound (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide has been synthesized and characterized by IR, NMR and Uv-vis spectroscopies, and single-crystal X-ray diffraction technique. In addition, quantum chemical calculations employing density functional theory (DFT) method with the 6–311++G(d,p) basis set were performed to study the molecular, spectroscopic and some electronic structure properties of the title compound, and the results were compared with the experimental findings. There exists a good correlation between experimental and theoretical data. Enol-imine/keto-amine tautomerization mechanism was investigated in the gas phase and in solution phase using the polarizable continuum model (PCM) approximation. The energetic and thermodynamic parameters of the enol-imine?→?keto-amine transfer process show that the single proton exchange is thermodynamically unfavored both in the gas phase and in solution phase. However, the reverse reaction seems to be feasible with a low barrier height and is supported by negative values in enthalpy and free energy changes both in the gas phase and in solution phase. The solvent effect is found to be sizable with increasing polarity of the solvents for the reverse reaction. The predicted nonlinear optical properties of the compound are found to be much greater than those of urea.     

Nuclear quantum effects in calculated NMR shieldings of benzene; a Feynman path integral study

The Feynman path integral Monte Carlo approach has been coupled to the gauge including atomic orbital formalism in order to analyse the absolute magnetic shieldings of the benzene nuclei under the conditions of thermal equilibrium. The Hamiltonian employed in the derivation of ensemble averaged NMR quantities is of the Hartree-Fock type. The basis set used is of 6–31G quality. The spatial delocalization of the atoms leads to a deshielding of both types of benzene nuclei relative to the shieldings experienced at the minimum of the potential energy surface. This deshielding has to be traced back to bond length elongations in thermal equilibrium. The influence of the nuclear fluctuations on the NMR parameters of benzene is quantum driven up to temperatures of 400 K; classical fluctuations are of minor importance in this low-temperature window.     

Spectroscopic nuclear quadrupole moments

A ‘year-2001’ set of nuclear quadrupole moments, Q, is presented. Compared to the previous, ‘year-1992’ set, a major revision of the value or a considerable improvement of the accuracy is reported for ⁶ ₃Li, ₇N, ¹⁹ ₉F (197 keV, I = 5/2), ₁₁Na, ₁₃Al, ₂₁Sc, ₂₂Ti, ₂₆Fe (14 keV, I = 3/2 Mössbauer state), ₃₁Ga, ₃₂Ge, ⁷⁷ ₃₄Se (250 keV, I = 5/2 state), ₃₅Br, ₃₆Kr, ₃₇Rb, ₃₉Y, ₄₀Zr, ¹⁰⁰ ₄₅Rh, ₅₀Sn (24 keV, I = Mössbauer state), ₅₃I, ₅₄Xe, ₅₅Cs and ₈₃Bi.     

Laser-induced condensation in colloid—polymer mixtures

We study a mixture of hard sphere colloidal particles and non-adsorbing polymers exposed to a plane wave external potential which represents a three-dimensional standing laser field. With computer simulations and density functional theory we investigate the structure and phase behaviour using the simple Asakura-Oosawa model. For varying laser wavelength λ we monitor the emergence of structure in response to the external field, as measured by the amplitude of the oscillations in the one-body density distribution. Between the ideal gas limit for small λ and the bulk limit of large λ there is a non-monotonic crossover that is governed by commensurability of λ and the colloid diameter. The theoretical curves are in good agreement with simulation results. Furthermore, the effect of the periodic field on the liquid-vapour transition is studied, a situation that we refer to as laser-induced condensation. Above a threshold value for λ the theoretical phase diagram indicates the stability of a ‘stacked’ fluid phase, which is a periodic succession (in the beam direction) of liquid and vapour slabs. This partially condensed phase causes a splitting of the liquid-vapour binodal leading to two critical and a triple point. All our predictions should be experimentally observable for colloid-polymer mixtures in an optical resonator.     

Radiometry and Radiation Efficiency of Twisted Gaussian Schell-Model Sources

Wavefields endowed with the coherence-induced property of optical twist have recently attracted a good deal of theoretical and experimental attention. We present the generalized radiometric theory of fields generated by twisted Gaussian Schell-model sources. The effects introduced by the novel, rotationally symmetric, twist phenomenon in the radiant intensity, generalized radiance, radiant emittance (irradiance), and the radiation efficiency are assessed. The radiance becomes directionally skewed as a result of the twist, whereas the radiant intensity remains axially symmetric. The twist reduces the radiation efficiency and broadens the radiation distribution, in agreement with the notion that the twist decreases the effective coherence. Several special cases, such as quasihomogeneous sources, are analyzed in detail. The radiometric results, which are physically consistent with the superposition models of twisted sources, are demonstrated by illustrative examples.     

Finite-size scaling and power law relations for dipole-quadrupole interaction on Blume-Emery-Griffiths model

The Blume-Emery-Griffiths model with the dipole-quadrupole interaction ($ \ell = \frac{I} {J} $ \ell = \frac{I} {J} ) has been simulated using a cellular automaton algorithm improved from the Creutz cellular automaton (CCA) on the face centered cubic (fcc) lattice. The finite-size scaling relations and the power laws of the order parameter (M) and the susceptibility (χ) are proposed for the dipole-quadrupole interaction (ℓ). The dipole-quadrupole critical exponent δ_χ has been estimated from the data of the order parameter (M) and the susceptibility (χ). The simulations have been done in the interval $ 0 \leqslant \ell = \frac{I} {J}0 \leqslant 0.01 $ 0 \leqslant \ell = \frac{I} {J}0 \leqslant 0.01 for $ d = \frac{D} {J} = 0,k = \frac{K} {J} = 0 $ d = \frac{D} {J} = 0,k = \frac{K} {J} = 0 and $ h = \frac{H} {J} = 0 $ h = \frac{H} {J} = 0 parameter values on a face centered cubic (fcc) lattice with periodic boundary conditions. The results indicate that the effect of the ℓ parameter is similar to the external magnetic field (h). The critical exponent δ_ℓ are in good agreement with the universal value (δ _h = 5) of the external magnetic field.