Effects of metal ion on the water structure studied by the Raman O?H stretching spectrum

Raman spectra in the O H stretching region of aqueous salt solutions were measured and compared, and the effects of metal ions on water structure deduced. The effects of alkali ions, alkaline ions or the first‐row transition metals on water structure were found to be similar. Differences of metal ionic effects on water structure exist among Na⁺, Mg²⁺ and Al³⁺, and between Ca²⁺ and Mn²⁺ and Al³⁺ and Fe³⁺. The factors that influence the metal ionic effects on the water structure are the ionic charge, the outmost electronic structure and ionic size, the ionic charge being the most important. With a five‐component Gaussian deconvolution of the Raman spectra of the aqueous solutions of NaCl, MgCl₂, AlCl₃ and FeCl₃ with concentrations of 0 to ∼1mol/l, the ionic effects were found to be similar on the bands at 3233, 3393, 3511 and 3628 cm⁻¹, but different on the band at 3051 cm⁻¹. With increasing polarization of the metal ion, the band at 3051 cm⁻¹, due to strong hydrogen bonding, increases. Copyright © 2009 John Wiley & Sons, Ltd.     

Insulator-conductor transition in liquid aluminium trichloride

We report molecular-dynamics simulations of ionic structure and diffusion in a pseudoclassical model of AlCl₃ over a wide region of the pressure-temperature (p,T) plane. The model melts from a layer crystal into a molecular liquid at low (p,T) and into a dissociated ionic liquid at high (p,T), in accord with x-ray diffraction studies of the AlCl₃ material. We show that pressure drives a broad liquid-liquid transition from a molecular insulator to an ionic conductor and trace the transition line in the (p,T) plane. This line has a negative dp/dT slope and appears to branch out from an anomaly in the melting curve.     

Structural studies of phase transitions in crystalline and liquid halides (ZnCl<Subscript>2</Subscript>, AlCl<Subscript>3</Subscript>) under pressure

The results of investigating the phase diagrams of ZnCl₂ and AlCl₃ halides, as well as the structure of the shortrange order of the corresponding melts under pressures up to 6.5 GPa, by the method of energy-dispersive x-ray diffraction are reported. When a ZnCl₂ crystal is compressed, a phase transition occurs from the γ phase (HgI₂ structure type) to the δ phase (distorted CdI₂ structure, WTe₂ type). The structural studies of the liquid state of ZnCl₂ and AlCl₃ indicate that the intermediate-range order decreases rapidly in the tetrahedral network of both melts as the pressure increases to 1.8 and 2.3 GPa for ZnCl₂ and AlCl₃, respectively. With further compression, the transitions in both melts occur with a change in the structure of the short-range order and with an increase in the coordination number. In this case, the transition in AlCl₃ occurs at ≈4 GPa and is a sharp first order transition, whereas the transition in ZnCl₂ occurs more smoothly in a pressure range of 2–4 GPa with a maximum intensity near 3 GPa. Thus, the AlCl₃ and ZnCl₂ compounds exemplify the existence of two phenomena—gradual decay of intermediate-range structural correlations and a sharper liquid-liquid coordination transition.     

Structure of negative impurity ions in liquid helium

The experimental mobilities of negative halogen (Cl^?, F^?, and I^?) and metal (Ba^? and Ga^?) impurity ions in superfluid ⁴He are close to each other and much lower than the mobilities of not only He⁺ ions but also electron bubbles. It has been shown that the formation of multiatomic complexes (clusters or bubbles) around ions is responsible for this low mobility. Although the mobilities are similar, the structures of the resulting complexes are qualitatively different in the cases of halogens and metals: solid clusters, which are similar to a well-studied cluster at the He⁺ ion, are formed near halogen ions, which exhibit high electron affinities, whereas metal ions are localized in bubbles, which are similar to electron bubbles. The temperature and pressure dependence of the mobility of these complexes is qualitatively different. Experiments in this area, most likely, performed with a wider variety of negative ions, would enhance the understanding of the structure of charged complexes in liquid helium.     

Interaction of ionic liquids with the surface of silica gel using nanocluster approach: a combined density functional theory and experimental study

Silica gel‐confined ionic liquid (IL) is a class of heterogeneous catalysts with broad catalytic applications. Leaching of the IL from the surface of the support is the major drawback of these catalysts, which reduce the catalyst efficiency during the chemical reactions. To investigate the effect of the hydrogen bonding on the leaching phenomena, the interaction between the 1‐ethyl‐3‐methylimidazolium‐based IL with various anions (Cl^?, Br^?, HSO₄^?, NO₃^?, BF₄^?, and PF₆^?) and the surface of the silica gel were studied using density functional theory. Hence, a hydroxylated cage‐like cluster of silica gel, Si₄O₆(OH), was selected to mimic the surface. The values of ΔE_interaction show that ILs with halogen counter ions have stronger interactions than that of the IL with BF₄^? and PF₆^? counter ions. We also carried out stirring–filtration method for some prepared samples of IL@silica to experimentally explore the leaching phenomena. The results show good agreement with computational achievements. Copyright © 2013 John Wiley & Sons, Ltd.     

Specific heat and transport properties of UPt3

We have determined partial radial distribution functions describing the distribution of ions around anions and around cations in -AgI at 573 K by measuring the diffuse neutron scattering and using the method of isotopic substitution on the silver ions. The results show that it is necessary to consider all three partial diffuse structure factors (A ₊₊,A _+–, andA _––) and not just two (A ₊₊ andA _+–) as has been done previously. The pair distribution functions show that the short range order in displacements of ions from the lattice sites appears remarkably similar to the short range order in molten CuCl. Of particular note is the similarity of the Ag–Ag and the Cu–Cu correlations which show very little structure.     

Reactive scattering of alkali dimers: chemi-ionization

Measurements of total cross sections Q_i for chemi-ionization in scattering of a K₂ dimer beam by a range of halogen containing molecules, at translational energies E ～ 7–11 kcal mol^-1, are reported. Substantial cross sections, Q_i ～ 2–10 Ų are exhibited by the halogen molecules Br₂, ICl, IBr, I₂. Distinctly lower values Q_i ～ 0·1–0.2 Ų are exhibited by BrCN and the mercuric and stannic halides, HgX₂, SnX₄. The results show a close correlation with the chemi-ionization exoergicities, particularly for formation of a K⁺,X^- ion pair. These chemi-ionization data and results from previous reactive scattering studies are compared, in order to estimate relative reaction yields for different reaction paths. The reaction dynamics for K₂ with halogen molecules and cyanohalides are rationalized in terms of the electronic structure of the potential surface, where the orientation of the K₂ dimer plays a crucial role.     

Photocatalytic activity and characterization of sol-gel-derived Cr(III)-doped TiO2-coated active carbon composites

Cr(III)-doped, TiO₂-coated active carbon (Cr–TiO₂/AC) were prepared by a sol–gel method. The effect of supports, including TiO₂ and active carbon (AC), on the molecular structure and photocatalytic activity of chromium oxide for complete decomposition of EDTA has been examined with respect to the content of Cr on the catalyst surface. The photocatalytic activity of the Cr–TiO₂/AC composites was evaluated in the decomposition of EDTA solution under UV irradiation. The results indicate that Cr–TiO₂/AC has a higher efficiency in decomposition of EDTA than TiO₂, TiO₂/AC or active carbon. This was attributed to the different functions of active carbon and chromate species. (1) Nanosize TiO₂ particles on composites were not reunited, possible because active carbon retards transformation of anatase into rutile and decreases the crystallite size. (2) Production of high concentrations of organic compound near Cr–TiO₂. (3) Carbon in active carbon causes some of the TiO₂ to reduce to Ti³⁺ ions, which prevents electron–hole pair recombination. (4) Formation of polychromate species, with a stronger redox capability, on the surface of TiO₂/AC. It was found that the addition of Cr to TiO₂ sol could suppress the grain growth of TiO₂ crystals and increase the hydroxyl content on the surface of TiO₂/AC. The photocatalytic efficiency and activity of the composites remained good, even after three cycles.     

Quantum theory of pure liquid metals as two-component systems

With the ultimate aims of clarifying the interpretation and the utility of effective ion-ion interactions in liquid metals, and of understanding the unusual isotopic mass dependence of the shear viscosity of liquid metal Li, a fully quantum statistical mechanical theory is developed from the many-body Hamiltonian of the conduction electron-positive ion assembly.We have set up quantum equations of motion which are analogs of classical continuity and conservation equations by expanding the equation for the Wigner distribution function about its diagonal. The most important of these equations for our present purposes relates the time derivative of the current density j(r, t) to the flux of current and to density-density correlation functions for electrons, electron-ions, and ions.This theory is then applied to neutron scattering by liquid metals. While the theory is sufficiently general in principle to treat electron-ion interaction of arbitrary strength, it is shown that when the interacion is weak, the usual results are recovered, along with the effective ion-ion interaction. In this latter connection, it is also demonstrated how the effective Ornstein-Zernike function C(q) in a liquid metal is related to bare ion and bare electron direct correlation functions and to the bare electron partial structure factor. Combining C(q) with one of the classical equations of liquid structure such as Born-Green or Percus-Yevick then relates the effective ion-ion interaction to the partial correlation functions of the bare ions and electrons.It is further shown how gradient expansions of the correlation functions lead to equations of motion for the density, current, and energy density which are simply the hydrodynamic equations of the present quantum theory of two-component systems. It is pointed out that the analog of the Navier-Stokes equation for the two-component system may be used to identify the quantity $\text{4}\text{3}\text{η + ζ}$ for the liquid metal, η and ζ being respectively the shear and bulk viscosities. Finally, it is demonstrated that $\text{4}\text{3}\text{η + ζ}$ depends explicitly on functional derivatives of the nonequilibrium pair distribution functions of ion-ion, electron-ion, and electron-electron correlations.     

Optical,thermal, and structural properties of Nb2O5–TeO2 and WO3–TeO2 glasses

Glass samples from two systems, Nb₂O₅–TeO₂ and WO₃–TeO₂, were prepared at two melt quenching rates and characterized by density, DSC, UV-visible, and Raman spectroscopy. Addition of Nb₂O₅ decreased the density while increase in the WO₃ concentration increased the density. Glasses prepared at higher quenching rates had smaller densities than glasses of the same composition prepared at lower quenching rate although the short-range structure of both glasses were identical, as revealed by Raman spectroscopy. Optical studies found an intense absorption band just below the absorption edge in both the glass series. This band was attributed to electronic transitions of Nb⁵⁺ and W⁶⁺ ions and a lone pair of electrons on Te atoms. Glass transition temperature increased with increase in Nb₂O₅ and WO₃ mol% due to the increase in average bond strength in the glass network. Raman spectroscopy showed that the concentration of TeO₄ units decreased with the increase in Nb₂O₅ and WO₃ concentrations.     

Zn2+-Schiff’s Base Complex as an “On–Off-On” Molecular Switch and a Fluorescence Probe for Cu2+ and Ag+ Ions

The present study presents a thorough theoretical analysis of the electronic structure and conformational preference of Schiff’s base ligand N,N-bis(2-hydroxybenzilidene)-2,4,6-trimethyl benzene-1,3-diamine (H₂L) and its metal complexes with Zn²⁺, Cu²⁺ and Ag⁺ ions. This study aims to investigate the behavior of H₂L and the binuclear Zn²⁺ complex (1) as fluorescent probes for the detection of metal ions (Zn²⁺, Cu²⁺ and Ag⁺) using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The six conformers of the H₂L ligand were optimized using the B3LYP/6–311?+??+?G** level of theory, while the L^?2-metal complexes were optimized by applying the B3LYP functional with the LANL2DZ/6–311?+??+?G** mixed basis set. The gas-phase and solvated Enol-cis isomer (E-cis) was found to be the most stable species. The absorption spectra of the E-cis isomer and its metal complexes were simulated using B3LYP, CAM-B3LYP, M06-2X and ωB97X functionals with a 6–311?+??+?G** basis set for C, O, N and H atoms and a LANL2DZ basis set for the metal ions (Zn²⁺, Cu²⁺ and Ag⁺). The computational results of the B3LYP functional were in excellent agreement with the experimental results. Hence, it was adopted for performing the emission calculations. The results indicated that metal complex (1) can act as a fluorescent chemosensor for the detection of Ag⁺ and Cu²⁺ ions through the mechanism of intermolecular charge transfer (ICT) and as a molecular switch “On–Off-On” via the replacement of Cu²⁺ by Ag⁺ ions, as proved experimentally.

     

熔体初始温度对液态金属Na凝固过程中微观结构影响的模拟研究

采用分子动力学方法对熔体初始温度热历史条件对液态金属Na凝固过程中微观结构的影响，进行了模拟研究，并采用双体分布函数g(r)曲线、键型指数法和原子团类型指数法对凝固过程中的微观结构进行了分析.结果表明：液态金属Na在不同熔体初始温度条件下以1×10¹¹K/s冷速凝固时，均形成晶化结构，其中1661和1441键型或体心立方基本原子团(14 6 0 8)在凝固过程中对微观结构的转变起决定性作用.同时发现：熔体初始温度对凝固微结构有显著影响，而对液态和过冷态的微观结构影响并不明显，只有在晶化起始温度T_c附近才充分地展现出来.不同熔体初始温度对凝固结构的晶化程度有不同的影响，虽其影响程度是随着熔体初始温度的下降呈非线性变化关系的，但仍表明是可以通过改变熔体初始温度来加以控制的.原子团类型指数法(比键型指数法)更进一步表征了晶化体系中原子团的结构特征，将有利于对液态金属凝固过程中微观结构的转变机理进行更为深入的研究.     

Solvation structure of magnesium,zinc, and alkaline earth metal ions in N,N‐dimethylformamide,N,N‐dimethylacetamide,and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

The solvation structure of magnesium, zinc(II), and alkaline earth metal ions in N,N‐dimethylformamide (DMF) and N,N‐dimethylacetamide (DMA), and their mixtures has been studied by means of Raman spectroscopy and DFT calculations. The solvation number is revealed to be 6, 7, 8, and 8 for Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, respectively, in both DMF and DMA. The δ (O C N) vibration of DMF shifts to a higher wavenumber upon binding to the metal ions and the shift Δν(= ν_bound − ν_free) becomes larger, when the ionic radius of the metal ion becomes smaller. The ν (N CH₃) vibration of DMA also shifts to a higher wavenumber upon binding to the metal ions. However, the shift Δν saturates for small ions, as well as the transition‐metal (II) ions, implying that steric congestion among solvent molecules takes place in the coordination sphere. It is also indicated that, despite the magnesium ion having practically the same ionic radius as the zinc(II) ion of six‐coordination, their solvation numbers in DMA are significantly different. DFT calculations for these metalsolvate clusters of varying solvation numbers revealed that not only solvent–solvent interaction through space but also the bonding nature of the metal ion plays an essential role in the steric congestion. The individual solvation number and the Raman shift Δν in DMF–DMA mixtures indicate that steric congestion is significant for the magnesium ion, but not appreciable for calcium, strontium, and barium ions, despite the solvation number of these metal ions being large. Copyright © 2006 John Wiley & Sons, Ltd.     

Charged-soft-sphere potentials for trivalent metal halides

Summary Octahedral-type coordination by halogens in the liquid state has been reported for a number of trivalent metal ions from diffraction and Raman scattering experiments on their molten trihalides and from Raman scattering spectroscopy of liquid mixtures of trihalides with alkali halides. We analyse the available data on bond lengths and Raman frequencies by treating an isolated (MX₆)³⁻ species within a model which adopts charged-soft-sphere interionic potentials supplemented by an account of ionic polarization. The trivalent metal ions that we consider are M=La, Ce, Pr, Nd, Sm, Gd, Dy and Y for X=Cl and M=Al for X=F. The main result of the analysis is the prediction of trends in the soft-sphere repulsive parameters for the trivalent metal ions, leading to estimates of all the vibrational frequencies and the binding energy of such octahedral species. Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction.     

Critical point and mechanism of the fluid–fluid phase transition in warm dense hydrogen

The density functional theory is used to calculate the equation of state and the proton–proton pair correlation functions in the range of hydrogen temperatures and densities where the fluid–fluid phase transition is expected. The metastable states are considered. The critical temperature has been estimated to be ~4000 K. We propose a two-step mechanism: the partial ionization of molecules to produce H ₂ ⁺ ions at the phase transition followed by the formation of H ₃ ⁺ ions.     

Partial pair correlation functions and viscosity of liquid Al–Si hypoeutectic alloys via high-energy X-ray diffraction experiments

The liquid structure of Al–Si hypoeutectic binary alloys was characterized by diffraction experiments using a high-energy X-ray (synchrotron) beam source. The diffraction experiments were carried out for liquid pure Al, Al–3?wt% Si, Al–7?wt% Si, Al–10?wt% Si and Al–12.5?wt% Si alloys at several temperatures. The salient structure information such as structure factor (SF), pair distribution function (PDF), radial distribution function (RDF), coordination number (CN) and atomic packing densities (PD) were quantified as a function of Si concentration and melt temperatures. Reverse Monte Carlo (RMC) analysis was carried out using the diffraction experimental data to quantify the partial pair correlation functions, such as partial structure factor, partial pair distribution function (PPDF) and partial radial distribution function. Furthermore, the partial pair distribution function and the liquid atomic structure information were used in a semi-empirical model to evaluate the viscosity of these liquid alloys at various melt temperatures. The results show that the viscosity determined by semi-empirical methods using the atomic structure information is in good agreement with the experimentally determined viscosity values.     

Metal ion interaction with ribosomal RNA

Summary We have used UV differential spectroscopy in order to detect small modifications in the ribosomal RNA absorption spectrum due to the binding of rRNA molecules with the metal ions Na⁺, K⁺, Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺ and Ni²⁺. Our data show that all the ions, investigated are involved in ion-type bond with the phosphate groups of rRNA and cause a refolding of the molecules with an overall increase in basebase ?stacking? interactions. Besides this ion-type binding with phosphate groups, transition metal ions Mn²⁺, Co²⁺, and Ni²⁺ are also able to bond directly to the bases To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

FA(Ga+,In+,Tl+) tunable laser activity and interaction of halogen atoms (F,Cl,Br,I,At) at the (001) surface of KCl crystal: ab initio calculations

An attempt has been made to examine F_A(Ga⁺,In⁺,Tl⁺) tunable laser activity and adsorptivity of halogen atoms (F,Cl,Br,I,At) at the (0 0 1) surface of KCl crystal using an embedded cluster model, CIS and density functional theory calculations with effective core potentials. The ion clusters were embedded in a simulated Coulomb field that closely approximates the Madelung field at the host surface. The nearest neighbor ions to the defect site were then allowed to relax to equilibrium. Based on the calculated strength of electron–phonon coupling and Stokes-shifted optical transition bands, The F_A(Tl⁺) center was found to be the most laser active in agreement with the experimental observation that the optical emissions of F_A(In⁺) and F_A(Ga⁺) centers were strongly quenched. The disappearance of the anisotropy and np splitting observed in the absorption of F_A(Ga⁺,In⁺,Tl⁺) centers were monotonically increasing functions of the size of the impurity cation. The F_A(Ga⁺,In⁺,Tl⁺) defect formation energies followed the order F_A(Ga⁺)>F_A(In⁺)>F_A(Tl⁺). The Glasner–Tompkins empirical relationship between the principal optical absorption of F centers in solids and the fundamental absorption of the host crystal was generalized to include the positive ion species. As far as the adsorptivity of the halogen atoms is concerned, the F and F_A(In⁺,Tl⁺) centers were found to change the nature of adsorption from physical adsorption to chemical adsorption. The adsorption energies were monotonically increasing functions of the electronegativity of the halogen and the amount of charge transferred from the defect-free surface. The calculated adsorption energies were explainable in terms of the electron affinity, the effective nuclear charge and the electrostatic potentials at the surface. The spin pairing mechanism played the dominant role in the course of adsorbate–substrate interactions and the KCl defect-free surface can be made semiconducting by F or F_A(In⁺,Tl⁺) surface imperfections.     

Structure and thermodynamic properties of positive and negative cluster ions in saturated vapour over barium dichloride

Geometrical structure, vibration spectra, and enthalpies of dissociation have been investigated for the ions BaCl₃^?, Ba₂Cl₃⁺, Ba₃Cl₅⁺, and Ba₄Cl₇⁺ which were detected earlier in the saturated vapour over BaCl₂. Quantum chemical methods of density functional theory, the second and the fourth order Møller–Plesset perturbation theory have been applied. The effective core potential with cc-pVTZ basis set for barium atom and two full-electron basis sets including the diffuse and polarised basis functions for chlorine atom were used. The effect of the basis set size and the computation method on the results was analysed. According to the results, all the ions possess the compact shaped structure. The equilibrium geometrical structures were found as follows: the planar D_3h for BaCl₃^?, triple bridged bipyramidal D_3h for Ba₂Cl₃⁺, hexabridged D_3h for Ba₃Cl₅⁺, and septuple bridged C_2v for Ba₄Cl₇⁺. For positive ions, the different isomeric structures were considered, but no isomers for these ions have been found. The geometrical parameters and vibration frequencies were utilised for computing of thermodynamic functions of the ions, and then the thermodynamic functions were used for the treatment of the experimental mass spectrometric data. The enthalpies of formation Δ_fH°(0 K) of the ions were determined (in kJ/mol): ?994 ± 6 (BaCl₃^?), ?481 ± 10 (Ba₂Cl₃⁺), ?1276 ± 14 (Ba₃Cl₅⁺), ?2048 ± 35 (Ba₄Cl₇⁺).     

Structures of CsMgBr3, CsCdBr3 and CsMgI3— diamagnetic linear chain lattices

The diamagnetic salts, CsMgBr₃, CsCdBr₃ and CsMgI₃, are shown by X-ray diffraction studies to adopt the CsNiCl₃ structure. This hexagonal lattice possesses a distinct one-dimensional character. The divalent metal ions in these salts are surrounded by octahedral arrays of halide ions ; however, there is a noticeable trigonal distortion. The structures are compared with those of other one-dimensional AMX₃ salts.