Spectral characteristics of water clusters in the interaction with ozone molecules and bromide ions

The molecular dynamics method is used to study the interaction of the (Br⁻) _i (H₂O)_{50 − i} clusters in a medium of water vapor with ozone molecules. The clusters absorb O₃ molecules and retain them, along with Br⁻ ions, for a 25-ps-long calculation procedure. The presence of bromide ions results in significant increases in the values of the real and imaginary parts of the relative permittivity. The addition of bromide ions causes a significant increase in the integrated IR radiation absorption intensities and in the radiant power emitted by the clusters. The addition of Br⁻ ions only slightly affects the intensity of the Raman spectra until the number of Br⁻ reaches six, when a dramatic decrease of the integrated intensity of this spectrum occurs. Bromide ions absorbed by water clusters produce a much more lasting impact on the ozone molecules trapped by the cluster than chlorine ions do, all other things being equal.     

Ion and solvent transport in polypyrrole: Experimental test of osmotic model

Ion and solvent transport in the conjugated polymer actuator material, polypyrrole doped with the immobile anion dodecyl benzene sulphonate, has been investigated by simultaneous cyclic voltammetry and Electrochemical Quartz Crystal Microbalance measurements. The purpose was to elucidate the precise nature of the mobile species during redox cycling, and to seek confirmation for the osmotic mechanism of actuation. Three testable aspects of the model were confirmed: The number of inserted H₂O molecules decreases with electrolyte concentration; at the same time the mechanism gradually changes from almost pure cation transport to ca. equal amount of anion transport; exchanging Br⁻ for Cl⁻ ions has only negligible effect at lower concentrations at equal osmotic pressures. Approximately, 4 H₂O molecules are tightly bound to each Na⁺ ion at concentrations <1 M. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Vibrational studies of spinel LixMn2O4 (0.3≤x≤1.0) cathodes

We report on the vibrational properties of spinel LiMn₂O₄ and its electrochemically delithiated forms Li_xMn₂O₄. Raman scattering and infrared absorption spectra have been studied as a function of the delithiation content in the wavenumber range 50–700 cm⁻¹. Results show that lithium ions can be extracted at room temperature to obtain Li_x[Mn₂]O₄ (0.3≤x≤1.0) without disrupting the [Mn₂]O₄ array. The normal modes of the spinel LiMn₂O₄ have been discussed in the O _h ⁷ symmetry and vibrations due to lithium ions with their oxygen neighbors have been identified at ca. 400 cm⁻¹. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

On the study of ion-acoustic solitary waves and double-layers in a drift multicomponent plasma with electron-inertia

Using the pseudopotential method, theoretical investigation has been made on the firstorder Korteweg-deVries ion-acoustic solitons in a multicomponent plasma consisting of warm positive ions, negative ions and isothermal electrons. The effects of electron-inertia and drift motion of the ions on the amplitudes and widths of the solitons have been studied in a plasma having (H⁺, Cl⁻), (H⁺, O⁻), (He⁺, H⁻) and (He⁺, O⁻) ions. Ion-acoustic double-layers have also been investigated for such plasmas. It has been found that drift velocity and electron-inertia have significant contribution on the formation of double-layers in multicomponent plasma     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Low temperature NMR study of cadmium-substituted copper ferrite

NMR spectra of Cd_XCu_1−xFe₂O₄ /0≤x≤0.30/ at liquid helium temperature have been obtained in the frequency range of 50 to 110 MHz using the spin-echo technique. Influence of substitution of Cu²⁺ ions by Cd²⁺ ions on effective magnetic fields at⁵⁷Fe nuclei has been found only at octahedral sites.     

EPR studies of Cu2+ and V4+ ions in phosphate glasses

Two lead-phosphate glass systems doped with both copper and vanadium ions in different ratios were studied by EPR (electron paramagnetic resonance) method. EPR spectra and parameters (g_‖ = 2.44, g_⊥ = 2.08 andA _‖ = 117.6 · 10⁻⁴ cm⁻¹) obtained for x(CuO · V₂O₅)(l−x)[2P₂O₅ · PbO] glasses withx ≤ 10 mol% suggest a tetrahedral (Td) coordination of Cu²⁺ ions and not a tetragonally elongated octahedron as has been assumed in previous works. The ground state of the paramagnetic electron is thed _xy copper orbital with a 4p_z contribution of 6%. For 20 ≤x ≤ 40 mol% a broad line (ΔB = 307 G) characteristic for clustered ions appears atg = 2.18. The V⁴⁺ ions are evidenced only in the spectra of x(CuO · 2V₂O₅)(1 −x)[2P₂O₅ · PbO] glasses and the resonance parameters suggest a pentacoordinated C_4v local symmetry for these ions. The hyperfine structures characteristic for Cu²⁺ and V⁴⁺ ions disappear for 10 ≤x ≤ 40 mol% due to the mixed exchange Cu²⁺−V⁴⁺ pair formation in these glasses.     

Formation and quenching mechanisms of excited particles in an oxygen-iodine laser medium

New values of a number of kinetic constants of processes proceeding in oxygen-iodine laser media are presented. The total probabilities of formation of I₂(X, 15 ≤ v ≤ 24) and I₂(X, 25 ≤ v ≤ 47) molecules in the course of quenching of I* atoms by I₂(X) are found to be 0.9 and 0.1, respectively. The quantum yield of singlet oxygen in the reaction O(¹ D) + N₂O → N₂ + O₂(a ¹Δ) is close to 100%. The quenching rate constants of I₂(A’) by O₂, H₂O, CO₂, I₂, and Ar and of I(² P _1/2) by O(³ P), O₃, NO₂, N₂O₄, and N₂O are presented.     

The infrared spectra of tutton salts 1. A comparative study of (NH4)2 M″(SO4)2·6H2O (M″=Ni,Co or Mg)

The infrared spectra of (NH₄)₂M″(SO₄)₂.6H₂O has been analysed in the region 4000–250 cm⁻¹. The dynamics of each crystal has been discussed in terms of 234 phonon modes, including 3 acoustical ones, using the unit cell approximation. The ambiguity in the assignments of the bands in the region 900–500 cm⁻¹ has been removed by assigning the bands in this region to the libratory modes of H₂O molecules. It has been concluded that the NH ₄ ⁺ and SO ₄ ²⁻ ions have a symmetry lower thanT _dand also the complex [M″(H₂O)₆]²⁺ has a symmetry lower than O _h . The hydrogen bonding is the strongest in the Ni-salt and the weakest in the Mg-salt.     

Europium-sensitized Chemiluminescence of System Tetracycline–H<Subscript>2</Subscript>O<Subscript>2</Subscript>–Fe(II)/(III) and Its Application to the Determination of Tetracycline

Chemiluminescence (CL) of the reaction system tetracycline–H₂O₂–Fe(II)/(III)–Eu(III) was used for the determination of tetracycline hydrochloride in water, pharmaceutical preparations, and honey. The CL spectrum registered for this system shows emission bands typical of Eu(III) ions, with a maximum at λ ∼ 600 nm, corresponding to the electronic transitions of ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂. A strong chemiluminescence intensity characteristic of europium(III) ions in the system tetracycline–H₂O₂–Fe(II)/(III)–Eu(III), as contrasted to the emission of the system tetracycline–H₂O₂–Fe(II)/(III) without Eu(III), proves that the Eu(III) ion plays the role of a chemiluminescence sensitizer, accompanying tetracycline oxidation in the Fenton system (H₂O₂–Fe(II)/(III)). A linear dependence was observed for the integrated CL light intensity on the tetracycline concentration in the range of 2 × 10⁻⁷ to 3 × 10⁻⁵ mol l⁻¹ with the detection limit of 5 × 10⁻⁸ mol l⁻¹ in aqueous solution.     

On the delay mechanism of Cl<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> diatomic anion dissociation up to the microsecond timescale

The dissociative capture of slow electrons by tetrachlorethylene (C₂Cl₄) has been investigated by resonant electron capture negative ion mass spectrometry. Metastable ions with fractional mass numbers 7.5, 17.5, and 19 corresponding to the C₂Cl₄⁻ → Cl⁻ + C₂Cl₃ and Cl₂⁻ → Cl⁻ + Cl decays occurring at the microsecond timescale have been detected. It has been revealed that Cl₂⁻ anions, which are fragment ions, can dissociate at the microsecond timescale, which is very surprising for a system with one internal degree of freedom. This process is assumingly attributed to the rotational excitation of Cl₂⁻ anions. Thus, the experimental estimate of the time of rovibronic relaxation in the Cl₂⁻ anion has been obtained.     

Electrical conductivity of BaCe0.9Nd0.1O3−α in H2+H2O+Ar gas mixture

Electroconductivity of BaCe_0.9Nd_0.1O_3−α was studied as a function of the composition of the H₂+H₂O+Ar mixture and temperature in the interval from 873 to 1173 K. It was shown that the electroconductivity was independent of P_H2 (0.97 to 0.10 atm) and P_O2 (10⁻²¹ to 10⁻²⁶ atm), but depended on P_H2O (0.08 to 0.005 atm). A mathematical processing of the P_H2O dependencies of the electroconductivity, which was performed in terms of a classical model of defect formation in high-temperature proton-conducting solid electrolytes, yielded equilibrium constants of the reaction of water dissolution in BaCe_0.9Nd_0.1O_3−α and mobilities of protons and oxygen ions. The temperature dependencies of these quantities were used to determine the mobility activation energies of protons (E_a=34±7 kJ/mole) and oxygen ions (E_a=72±8 kJ/mole), and also the enthalpy (ΔH=−150±25 kJ/mole) and the entropy (ΔS=153±26 kJ/mole·K) of the reaction of water dissolution in BaCe_0.9Nd_0.1O_3−α.     

Electron-stimulated desorption of negative O? ions from the oxidized O/Ru surface

This paper reports on a study of the electron-stimulated desorption of negative oxygen ions from the O/Ru surface, which represents an additional factor responsible for the destruction of the protective oxide layer of the mirrors used in ultraviolet lithography. The cross section of degradation of the O/Ru layer due to the electron-stimulated desorption of the O⁺ and O⁻ ions and the O atoms has been found to be 1.6 × 10⁻¹⁹ cm². A comparison of the dependences of the electron-stimulated desorption yield of O⁺ and O⁻ ions on the incident electron energy E with the ionization cross section of the adsorbate core level σ _O2s (E) has revealed that the ionization of the O 2s level is the main channel of the electron-stimulated desorption of O⁻ ions.     

Spectroscopic properties of 1.8 μm emission of thulium ions in germanate glass

A new type host of germanate glass (GeO₂− BaO−BaF₂−Ga₂O₃−La₂O₃) codoped with Tm₂O₃ has been investigated for application as laser material. It possesses a large emission cross section with the value of 9.3×10⁻²¹ cm² at 1.8 μm. Judd-Ofelt intensity parameters and radiative transition probability are calculated and analyzed by Judd-Ofelt theory and absorption spectra. The infrared emission spectra at 1.8 μm have been obtained by using a 794 nm laser diode as excitation resource. The emission intensity ratio of 1.8 (³F₄→³H₆) to 1.47 μm (³H₄→³F₄) increases, while the experimental lifetime of the Tm³⁺:³H₄ level decreases by increasing Tm₂O₃ concentration, which is attributed to the presence of a cross relaxation process. The most intensive emission at 1.8 μm is achieved from the germanate glass with the concentration of Tm₂O₃ reaches 1.0 wt%. The extended overlap integral method is used to calculate the microparameter of the energy transfer and the critical distance, which are derived to better understand the energy transfer process of thulium ions in the germanate glass responsible for emission at 1.8 μm.     

The metal-semiconductor transition monitored by excited state lifetimes of Al4O m − clusters

The lifetimes of electronically excited states of Al₄O _m ⁻ clusters are measured for m=1,3,4,5, and 6 using time-resolved photoelectron spectroscopy. With increasing number of oxygen atoms the lifetimes increase. This can be explained qualitatively by a metal-semiconductor transition occurring between the metal-like Al₄ ⁻ cluster and the fully oxidized semiconductor-like Al₄O₆ ⁻ cluster. Long lifetimes of electron-hole excitations are characteristic for semiconductors, while in metals the strong interaction between the delocalized electrons causes short lifetimes.     

Vibrational analysis of NaM2OH(H2O)(MoO4)2/D2O [M=Ni,Zn]

The infrared and Raman spectra of NaNi₂OH(H₂O)(MoO₄)₂ and NaZn₂OH (H₂O)(MoO₄)₂ and their partially deuterated analogues are recorded and analysed on the basis of vibrations of MoO ₄ ²⁻ tetrahedra and H₂O molecules. The MoO ₄ ²⁻ groups are found to be more distorted in NaNi₂OH(H₂O)(MoO₄)₂ than in the other compound. Bands indicating the presence of H₃O⁺ ions are not observed in NaZn₂OH(H₂O)(MoO₄)₂ ruling out the possibility of the formulation of NaZn₂OHO(MoO₃OH)₂. Hydrogen bonds of medium strength are present in both the compounds.     

Four-wave mixing spectroscopy of aqueous suspensions of single-wall carbon nanotubes in the ranges of 0.1–10 and 100–250 cm<Superscript>−1</Superscript>

Distinctive optical properties of single-wall carbon nanotubes (SWNT) are highly sensitive to variations in the environment. Here, we have studied SWNT in aqueous suspensions at a low (less than 0.1 μg ml⁻¹) concentration by four-wave mixing (FWM) spectroscopy in the spectral bands of 0.1 to 10 cm⁻¹ (≈300 GHz) and 100 to 250 cm⁻¹ (3 to 7.5 THz). We directly investigated the hydration layers around SWNT. A comparison of the FWM spectra of an SWNT aqueous suspension and Milli-Q water shows a considerable increase in the intensity of low-frequency Raman modes, which are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed phenomenon by the hydrogen peroxide production and formation of a low-density depletion layer at the water-nanotube interface. We have observed several SWNT radial breathing modes ω _RBM =118.5, 164.7, and 233.5 cm⁻¹ in an SWNT aqueous suspension and estimated the corresponding SWNT diameters as ≈2.0, 1.5, and 1 nm.     

Low frequency four-wave mixing spectroscopy of biopolymer hydration layers in aqueous solutions

Four-wave mixing (FWM) spectroscopy has been applied to detection of H₂O₂ molecules rotational resonances in both DNA and denatured DNA aqueous solutions in the range ±100 cm⁻¹. A considerable growth of rotational lines intensity of H₂O and H₂O₂ has been observed in comparison with distilled water. This fact was interpreted as an exhibition of specific property of a hydration layer formation at DNA/water and denatured DNA/water interfaces. The fitting of four-wave mixing spectra shows the increasing of the H₂O₂ rotational line’s amplitude by a factor of ∼3 in DNA solutions due to denaturizing. The shifting of FWM Brillouin resonances in opposite way in protein solution and SWNT (single wall carbon nanotube) suspension to comparison with water was observed and discussed.