Study of the ferroelectric–paraelectric phase transition of NaH3(SeO3)2 single crystals by H and Na NMR

The ¹H and ²³Na spin–lattice and spin–spin relaxation times of NaH₃(SeO₃)₂ single crystals grown using the slow-evaporation method were measured as functions of temperature and frequency in the ferroelectric and paraelectric phases. The changes in the symmetry of the (SeO₃)²⁻ dimers as a result of the ferroelectric–paraelectric phase transition are associated with large changes in the spin–lattice and spin–spin relaxation times, and in the number of resonance lines. The large changes in the relaxation times at 195 K indicate that the H and Na ions are significantly affected by this transition. The change in the number of resonance lines for the ¹H and ²³Na nuclei means that the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions change at T_C. Therefore, the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions play important roles in the phase transitions. In conclusion, the ferroelectric–paraelectric phase transition of NaH₃(SeO₃)₂ is accompanied by changes in hydrogen-bond structure and distortions of the (SeO₃)²⁻ and Na⁺ ion lattices, which form a slightly distorted octahedron.     

Desorption of small ionic fragments from oligonucleotides induced by low energy carbon ions

The degradation of oligonucleotide films containing differing base sequences induced by 4 keV C⁺ ions has been studied experimentally. The oligonucleotides were deposited onto a gold coated stainless steel substrate and the anions and cations released from the films were analyzed by a quadrupole mass spectrometer. The total ion desorption yield was recorded as a function of time using a constant C⁺ ion flux of 6 × 10¹⁴ ions cm^-2 s^-1. At low fluences the formation of small ionic fragments was observed, whilst for fluences greater than 1.2 × 10¹⁸ ions cm^-2 molecules were sputtered from the substrate. In addition to studies of the influence of a particular base to the total cation desorption yield, the effect of base substitution with bromine was measured for negative ion desorption. These results showed a strong degradation of oligonucleotide films during ion bombardment.     

Post-sintering annealing effect on the diffuse phase transition in (Pb1−xBax)(Yb0.5Ta0.5)O3 ceramics

The effect of post sintering annealing on the dielectric response of (Pb_1−xBa_x)(Yb_0.5Ta_0.5)O₃ ceramics in the diffuse phase transition range (x=0.2) has been investigated. The samples are prepared by conventional solid-state reaction method. The samples are sintered at 1300 °C for 2 h and annealed at different temperatures (800, 900 and 1000 °C) for 8 h and at 800 °C for different time durations (8, 12 and 24 h). A significant change in the dielectric response has been observed in all the samples. The dielectric constant increases remarkably and the dielectric loss tangent decreases. The dielectric peaks of the annealed samples are observed to be more diffused with noticeable frequency dispersion compared to the as sintered sample.     

Investigation of phase transition mechanisms of CsH3(SeO3)2 single crystals by observation of nuclear magnetic resonance

The relaxation times of the ¹H and ¹³³Cs nuclei in CsH₃(SeO₃)₂ crystals were investigated using FT NMR. The ¹³³Cs spectrum does change from seven resonance lines to one resonance line near T_m (=350 K). The presence of only one ¹³³Cs signal is due to the liquid state resulting from the melting of the crystal. The variation in the separation of the ¹³³Cs resonance lines with temperature indicates that the EFG at the Cs sites produced by the (SeO₃)²⁻ groups varies with temperature, which in turn means that the atoms neighboring ¹³³Cs are displaced. And, the T₁ for ¹³³Cs is very long and undergoes significant changes near T_m. The change in the temperature dependence of T₁ at T_m for the ¹³³Cs nuclei coincides with the melting temperature. These results are compared with those obtained for MH₃(SeO₃)₂ (M=Na, K, and Cs) crystals.     

Desorption of metastable species induced by electronic excitation at the surface of solid krypton with physisorbed hydrogen

The effect of the physisorbed hydrogen molecules on the electron stimulated desorption of metastables from the surface of solid Kr was investigated. At the clean surface of solid Kr, the desorption of Kr metastables occurs only through an excimer dissociation mechanism. Physisorption of hydrogen molecules causes the following effects: (1) the total desorption yield of the metastable species increased by an order of magnitude or more; (2) metastable Kr, which is probably desorbed through the cavity ejection mechanism, emerges; (3) metastable Kr by excimer dissociation is also enhanced; and (4) a new metastable species, which seems to be composed of metastable hydrogen molecule, appears.     

Carbon nanotubes supported Cu-Ni bimetallic catalysts and their properties for the direct synthesis of dimethyl carbonate from methanol and carbon dioxide

Multi-walled carbon nanotubes (MWCNTs) supported Cu-Ni bimetallic catalysts for the direct synthesis of dimethyl carbonate (DMC) from CH₃OH and CO₂ were synthesized and investigated. The supporting materials and the synthesized catalysts were fully characterized using FTIR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction (XRD) and X-ray photoelectron spectrum (XPS) techniques. The catalytic activities were investigated by performing micro-reactions. The experimental results showed that the metal phase and Cu-Ni alloy phase in the catalyst were partially formed during the calcination and activation step. Active metal particles were dispersed homogeneously on the surface of the MWCNTs. Cu-Ni/MWCNTs catalysts were efficient for the direct synthesis of DMC. The highest conversion of CH₃OH was higher than 4.3% and the selectivity of DMC was higher than 85.0% under the optimal catalytic conditions of 120 °C and around 1.2 MPa. The high catalytic activity of Cu-Ni/MWCNTs in DMC synthesis can be attributed to the synergetic effects of metal Cu, Ni and Cu-Ni alloy in the activation of CH₃OH and CO₂, the unique structure of MWCNTs and the interaction between the metal particles and the supports.     

On the mechanism of the sensitization of PADC (poly(allyl diglycol carbonate)) track detectors by carbon dioxide treatment

The sensitization effect of carbon dioxide treatments with 0.6 MPa on poly(allyl diglycol carbonate) (PADC) etched track detectors is confirmed for protons and He, C, and Fe ions, where the stopping powers range from 10 to 600 keV/μm. Based on the FT-IR study for the PADC films that were maintained at room temperature and at elevated temperatures, the diffusion coefficient of carbon dioxide, is determined as D = 14,670exp(−9030/T(K)) cm²/s. The sensitivity is enhanced when carbon dioxide is released toward the chemical etching solution that passes through the detector surface. Segmented PADC polymer chains are washed away by the flow of carbon dioxide along the latent tracks in PADC, which results in a higher track etch rate.     

Deactivation of Pd particles supported on Nb2O5/Cu3Au(1 0 0): SFG and TPD studies from UHV to 100 mbar

Structural changes that occur on Pd-Nb₂O₅/Cu₃Au(1 0 0) model catalysts upon thermal annealing were followed by sum frequency generation (SFG) and temperature-programmed desorption (TPD) using CO as probe molecule. SFG experiments were performed both under ultrahigh vacuum and mbar pressure. Heating the catalyst to temperatures above 300 K lead to an irreversible 50% decrease in the CO adsorption capacity and modified the remaining adsorption sites. Alterations of the phase between resonant and non-resonant SFG signals upon annealing indicate a change in the electronic structure of the surface, which excludes Pd sintering or migration of Nb₂O₅ over Pd particles to cause the observed effect and rather suggests the formation of “mixed Pd-NbO_x” sites. The same changes in surface properties also occur during CO hydrogenation at 1 bar and high temperature, pointing to an involvement of “mixed Pd-NbO_x” sites in catalytic reactions.     

Tuning the orthorhombic–rhombohedral phase transition temperature in sodium potassium niobate by incorporating barium zirconate

We report that the orthorhombic–rhombohedral phase transition temperature in sodium potassium niobate could be tuned from lower to higher than room temperature by incorporating barium zirconate into it. It is revealed that when barium zirconate is between 8 mol% and 15 mol%, the solid solution exhibits rhombohedral symmetry at room temperature. Rietveld analysis shows that the space group of the rhombohedral phase is R3m. It is suggested that a relatively larger B‐cation favors the low‐temperature phase which is a common phenomenon for perovskite ferroelectrics. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study on the phase transitions by nuclear magnetic resonance of α-type RbAl(SO4)2·12H2O and β-type CsAl(SO4)2·12H2O single crystals

The thermodynamic properties, spin–lattice relaxation times, T₁, and spin–spin relaxation times, T₂, of the ²⁷Al, ⁸⁷Rb, and ¹³³Cs nuclei in MAl(SO₄)₂·12H₂O (M=Rb and Cs) crystals were investigated, and the two crystals were found to lose H₂O with increases in temperature. From our results for T₁ and T₂, we conclude that the discontinuities near T_d in the T₁ curves of the two crystals correspond to structural changes. In both crystals, below T_d the water molecules surrounding the Al³⁺ and M⁺ nuclei form distorted octahedra, whereas above T_d the water molecules around the Al³⁺ and M⁺ nuclei form regular octahedra and the environment of the Al³⁺ and M⁺ nuclei has cubic symmetry. Further, the T₁ for the ²⁷Al and ⁸⁷Rb nuclei in RbAl(SO₄)₂·12H₂O below T_d were found to increase with increasing temperature, whereas the T₁ for the ²⁷Al and ¹³³Cs nuclei in CsAl(SO₄)₂·12H₂O were found to decrease. It is possible that this difference is due to the different characteristics of α- and β-type crystals.     

Adsorption of carbon monoxide Au/Pd(1 0 0) alloys in ultrahigh vacuum: Identification of adsorption sites

The adsorption of carbon monoxide is studied on Au/Pd(1 0 0) alloys by means of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). The alloy was formed by adsorbing a four-monolayer thick gold film on a Pd(1 0 0) substrate and by heating to various temperatures to form alloys with a range of palladium coverages. The alloy was characterized using X-ray photoelectron spectroscopy and the composition of the outermost layer measured using low-energy ion scattering spectroscopy. CO adsorbs on palladium bridge sites only for palladium coverages greater than 0.5 monolayers (ML) suggesting that next-nearest neighbor sites are preferentially populated by palladium atoms. CO adsorbs on atop palladium sites and desorbs at ∼350 K corresponding to a desorption activation energy of ∼117 kJ/mol. However, at lower palladium coverages, these sites are not occupied and CO desorption states are detected 170 and 112 K corresponding to desorption activation energies of ∼53 kJ/mol and ∼35 kJ/mol, respectively, for these states. It is suggested that these states are due to a restructuring of the surface to form low-coordination gold sites that obscure the atop palladium site.     

Line profile study of transitions in the 30012 ← 00001 and 30013 ← 00001 bands of carbon dioxide perturbed by air

In this work we present a line profile study for air-broadened carbon dioxide transitions in the 30012 ← 00001 and 30013 ← 00001 vibrational bands. The room temperature spectra were recorded at a resolution of 0.008 cm⁻¹ using a Fourier Transform spectrometer. The air-broadening, air-shift, and air-line mixing coefficients were derived from a simultaneous fitting of spectra using the Voigt model and a Speed-Dependent Voigt lineshape model. The results obtained are consistent with other studies in addition to the theoretically calculated values. Exponential Power Gap (EPG) and Energy Corrected Sudden (ECS) scaling laws were used to calculate the relaxation matrix elements.     

Sulphur dioxide insertion into tin―carbon bonds: solvent effects and the nature of the transition state

Data describing the insertion of sulphur dioxide into the carbon―tin bond of a range of substituted phenyltrimethyltin compounds in methanol and benzene solvents have been reconsidered. The reaction in methanol is cleanly second order, but the reaction in benzene has both a second‐order and third‐order component, the latter ascribable to an initial equilibrium formation of a SO₂ complex with the phenyl ring followed by the insertion of a second SO₂ molecule into the carbon–tin bond. Molecular orbital calculations have identified the transition states (TS) and the favoured reaction pathways for the second‐order and third‐order reaction pathways in benzene. The effects of solvents on TS and enthalpies of reaction have also been examined. New insights into the types of TS involved in electrophilic substitution reactions are revealed. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermodynamics approach of the formation of Ni catalyst particles for carbon nanotubes growth

Size-dependent thermodynamic parameters, such as Gibbs free energy, enthalpy and entropy, for the transition of a Ni nanofilm to catalyst particles for subsequent carbon nanotube growth have been explored. In this investigation, we consider the derived equations of the size-dependent melting temperature of nanosolids based on our previous works. Using this thermodynamic approach, it is found that the diameter of Ni particles is 3 times greater than the thickness of the original film. From the critical and stable sizes of transformed Ni nanoparticles, a minimum film thickness for transformation of film to nanoparticles was obtained. Our predictions are in good agreement with experimental results.     

The role of carbon impurities on the Si(0 0 1)-c(4 × 4) surface reconstruction: Theoretical calculations

In this work we employ the state-of-the-art pseudopotential method, within a generalized gradient approximation to the density functional theory, combined with a recently developed method for the calculation of HREELS spectra to study a series of different proposed models for carbon incorporation on the silicon (0 0 1) surface. A fully discussion on the geometry, energetics and specially the comparison between experimental and theoretical STM images and electron energy loss spectra indicate that the Si(1 0 0)-c(4 × 4) is probably induced by Si-C surface dimers, in agreement with recent experimental findings.     

Effect of glycine substitution on the ferroelectric phase of betaine arsenate [(CH3)3NCH2COO·H3AsO4]

The present work reports an experimental investigation on the influence of glycine (NH₂CH₂COOH) substitution in the polar properties and the critical dynamics of the molecular ferroelectric betaine arsenate, (CH₃)₃NCH₂COO·H₃AsO₄. The dielectric dispersion (20 Hz<ν<3 MHz) and the thermally induced displacement currents are investigated in detail over the extended Curie region of the system (130 K<T<100 K). The results obtained for a single crystal with nominal glycine content of 20% are analyzed, compared with those obtained for pure betaine arsenate and discussed within the scope of a phenomenological Landau model previously used to describe a system with competing ferroelectric and structural instabilities.     

Theoretical study of CO2 activation on Pt(111) induced by coadsorbed K atoms

The adsorption of CO₂ on the clean and potassium-precovered Pt(111) surface has been studied by means of the cluster model approach within the hybrid B3LYP density functional theory-based method. On the clean surface, CO₂ is undistorted and weakly bound. The equilibrium position of this physisorbed species appears at a rather large distance from the surface. However, when coadsorbed K atoms are included in the model, a chemisorbed, bent CO₂ species on top of a surface Pt atom is found. The presence of the coadsorbed K is found to be necessary to promote CO₂ chemisorption and activation, the key step in activating the CO₂ molecule being a direct interaction with the coadsorbate. In addition, the calculated vibrational frequencies for this chemisorbed species are in agreement with available experimental data.     

Adsorption of carbon monoxide on Pt{100} surfaces: dependence of the CO stretching vibrational frequency on surface coverage

We have used the ab initio cluster model approach to study the dependence of the CO stretching frequency on CO surface coverage. We have also investigated the relative importance of the various factors that can affect the position of the CO stretching band as coverage increases. Two effects can change the CO stretching frequency: the adsorbate–adsorbate dipole coupling, which is a purely physical effect, and the changes in the 2π^* CO molecular orbitals, due to the different chemical environment at higher coverages. From our vibrational analysis, we conclude that CO–CO dipole coupling is the main cause of the upward shift of the CO stretching band when the CO coverage is increased. The population of the 2π^* CO molecular orbitals does not change at any coverage within the region considered. We have also estimated the ¹²CO–¹³CO dipole coupling, which previous studies have assumed to be weak. Our results demonstrate that the ¹²CO–¹³CO dipole coupling is indeed weak compared with the ¹²CO–¹²CO dipole coupling. At a CO surface coverage of 0.5 monolayers (ML), we have calculated a band shift of 40 cm⁻¹ to higher frequency. However, we should point out that when one ¹²CO molecule is surrounded by a ¹³CO environment, the ¹²CO stretching band shifts 10 cm⁻¹ upwards. We have also computed the heat of adsorption of CO on Pt{100}-(1×1) as a function of CO coverage. The initial heat of adsorption is calculated to be about 192 kJ mol⁻¹ and then drops to 180 kJ mol⁻¹ at 0.5 ML. These results agree quite well with recent calorimetric measurements. Besides that, we have estimated that the CO–CO interaction energy at 0.5 ML is repulsive and has a value of 5 kJ mol⁻¹.