Atomic Displacements in the α–β Phase Transition in Ag 2 S and in Ag 2 S/Ag Heterostructure

Orientation relationships between low-temperature monoclinic semiconductor α-Ag2S acanthite and high-temperature body-centered β-Ag2S argentite are determined. It is shown that, in cubic argentite, possible distances between silver atoms are too small for the sites of the metal sublattice to be occupied by Ag atoms with probability equal to one. With regard to the possible arrangement of Ag atoms, it is shown that, during the “acanthite–argentite” transformation, the jump of a silver ion from site (e) of monoclinic acanthite to site (j) of cubic argentite is the most probable process. It is established that the acanthite–argentite transformation in Ag2S/Ag heteronanostructure is accompanied by the formation of a conductive channel of silver Ag and β-Ag2S argentite under the application of an external voltage. The on-to-off-state current ratio in the synthesized Ag2S/Ag heteronanostructure is approximately equal to 670. For the Ag2S/Ag heteronanostructure, the energy barrier for the hopping of an Ag+ ion from an atomic site of monoclinic acanthite to a site of cubic argentite is estimated.     

Argentite-Acanthite Transformation in Silver Sulfide as a Disorder-Order Transition

An alternative model has been proposed for the phase transition from cubic argentite ß-Ag₂S to monoclinic acanthite α-Ag₂S in silver sulfide as a disorder–order transition. It has been shown that, as the temperature decreases below the transition temperature T_trans, S atoms equiprobably occupying the sites of the body centered cubic (bcc) nonmetal sublattice of argentite are concentrated at four sites of the monoclinic nonmetal sublattice, whereas the other sites remain vacant. A disorder-order transition channel including three superstructure vectors of k₉ and k₄ stars has been determined. The distribution function of sulfur atoms in monoclinic acanthite α-Ag₂S has been calculated. It has been shown that displacements of sulfur atoms distort the bcc nonmetal sublattice of argentite, forming a monoclinic lattice, where silver atoms are spaced by quite large distances and occupy their crystallographic positions with a probability of 1. The region of allowed values of the long-range order parameters η₉ and η₄ for the model monoclinic ordered phase α-Ag₂S has been determined.

     

Thermal expansion of nanocrystalline and coarse-crystalline silver sulfide Ag<Subscript>2</Subscript>S

In situ studies of the thermal expansion of polymorphic phases of coarse-crystalline and nanocrystalline silver sulfide, namely, monoclinic acanthite α-Ag₂S and cubic argentite β-Ag₂S, have been performed for the first time by high-temperature X-ray diffraction. The temperature dependences of the unit cell parameters of acanthite and argentite have been measured from temperatures in the range of 300–623 K, and the thermal expansion coefficients of acanthite and argentite have been determined. The observed difference between the thermal expansion coefficients of nano- and coarse-crystalline acanthite is shown to be due to a small size of nanocrystalline silver sulfide particles, which leads to an increase in the anharmonicity of atomic vibrations.     

Polymorphic transformation in nanocrystalline silver sulfide

The α-Ag₂S acanthite–β-Ag₂S argentite phase transformation in nanocrystalline silver sulfide has been studied in situ for the first time using high-temperature X-ray diffraction and scanning electron microscopy. The formation of argentite has been proved by differential thermal analysis. The acanthite–argentite transformation occurs at a temperature of ～449–450 K, and its enthalpy is ～3.7–3.9 kJ mol^–1. The thermal expansion coefficients of acanthite and argentite have been estimated.     

Thermal expansion and the heat capacity of nanocrystalline and coarse-crystalline silver sulfide Ag2S

The thermal expansion and the heat capacity of coarse-crystalline and nanocrystalline silver sulfide Ag₂S were studied by dilatometry and differential scanning calorimentry for the first time in the temperature range 290–970 K. It is found that the thermal expansion coefficient and the heat capacity of nanocrystalline silver sulfide in this temperature range are higher than those in the case of the coarse-crystalline sulfide. It is revealed that the transformation of α-Ag₂S acanthite to β-Ag₂S argentite and β-Ag₂S argentite to γ-Ag₂S phase are the first-order phase transitions; the temperatures and the enthalpies of these transformations have been determined.

     

Ag<Subscript>2</Subscript>S/Ag heteronanostructure

An Ag₂S/Ag heteronanostructure has been prepared for the first time by hydrochemical deposition. The “acanthite α-Ag₂S–argentite β-Ag₂S” phase transformation has been studied in situ by high-temperature X-ray diffraction and transmission electron microscopy. The crystal structure of argentite has been revealed. It has been found that the concentration of vacant sites in the metal sublattice of argentite exceeds 92%. The reversible acanthite–argentite transformation in the Ag₂S/Ag heteronanostructure at the application of the external bias voltage is considered.     

Low Temperature Hydrogen Antihydrogen Interactions

In view of current interest in the trapping of antihydrogen ( ) atoms at low temperatures [1–3], we have carried out a full four-body variational calculation to determine s-wave elastic phase shifts for hydrogen antihydrogen scattering, using the Kohn Variational Principle. Terms outside the Born–Oppenheimer approximation have been taken into account using the formalism of Kołos and Wolniewicz [4]. As far as we are aware, this is the first time that these terms have been included in an H scattering calculation. This is a continuation of earlier work on H– interactions [5–7]. Preliminary results differ substantially from those calculated using the Born–Oppenheimer approximation [8–10]. A method is outlined for reducing this discrepancy and taking the rearrangement channel into account. This revised version was published online in August 2006 with corrections to the Cover Date.     

Anti-stokes luminescence of Zn<Subscript>0.6</Subscript>Cd<Subscript>0.4</Subscript>S solid solutions with adsorbed organic dye molecules and few-atom silver clusters

For microcrystals of Zn_0.6Cd_0.4S with adsorbed molecules of a number of organic dyes, we have observed sensitized anti-Stokes luminescence excited by radiation with wavelengths in the range 610–750 nm and flux density 10¹⁴–10¹⁵ photons/cm²·sec. The positions of the bands in the excitation spectra for such luminescence match those of the absorption spectra for the adsorbed dye molecules, which is evidence in favor of a cooperative mechanism for its appearance. We have shown that enhancement of the anti-Stokes luminescence is possible when silver atoms and few-atom clusters appear on the Zn_0.6Cd_0.4S surface in addition to the dye molecules. We hypothesize that its excitation in the latter case occurs as a result of two-photon optical transitions. These transitions occur sequentially, with transfer of an electron or the electronic excitation energy from the dye molecules to silver atoms and few-atom clusters adsorbed on the surface of Zn_0.6Cd_0.4S, creating deep localized states in the bandgap with photoionization energies 1.80–2.00 eV. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 617–621, September–October, 2007.     

Monoclinic superstructure V14O6 of the tetragonal solid solution of oxygen in vanadium

The monoclinic (space group C2/m) superstructure of V₁₄O₆, which is formed in the atom-vacancy ordering of the tetragonal solid solution of oxygen in vanadium, is studied by the methods of x-ray diffraction and symmetry analysis. It has been found that the channel of the order-disorder phase transition attributed to the formation of the monoclinic suboxide V₁₄O₆ includes six superstructure vectors belonging to three non-Lifshitz stars {k ₁₋₁}, {k ₁₋₂}, and {k _1–3} of one type {k ₁}. The distribution function of the O atoms in the V₁₄O₆ monoclinic superstructure has been calculated. It has been shown that the displacements of V atoms distort the body-centered tetragonal metal sublattice, thus preparing the formation of the fcc sublattice and the transition from the suboxide V₁₄O₆ to the cubic vanadium monoxide with the B1 structure. Original Russian Text ? A.I. Gusev, D.A. Davydov, 2007, published in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2007, Vol. 86, No. 10, pp. 746–751.     

Monoclinic superstructure V<Subscript>14</Subscript>O<Subscript>6</Subscript> of the tetragonal solid solution of oxygen in vanadium

The monoclinic (space group C2/m) superstructure of V₁₄O₆, which is formed in the atom-vacancy ordering of the tetragonal solid solution of oxygen in vanadium, is studied by the methods of x-ray diffraction and symmetry analysis. It has been found that the channel of the order-disorder phase transition attributed to the formation of the monoclinic suboxide V₁₄O₆ includes six superstructure vectors belonging to three non-Lifshitz stars {k ₁₋₁}, {k ₁₋₂}, and {k _1–3} of one type {k ₁}. The distribution function of the O atoms in the V₁₄O₆ monoclinic superstructure has been calculated. It has been shown that the displacements of V atoms distort the body-centered tetragonal metal sublattice, thus preparing the formation of the fcc sublattice and the transition from the suboxide V₁₄O₆ to the cubic vanadium monoxide with the B1 structure.     

Measurement of the K α to L α and K β to L β intensity ratios of seven elements in the atomic number range 52≤ Z ≤62 using photoionization at 59.5 keV1

The Kα to Lα and Kβ to Lβ intensity ratios of seven elements have been measured following photoionization at 59.5 keV by using a Si (Li) detector (FWHM=155 eV at 5.96 keV). The intensity ratios were determined by measuring K and L x-rays emitted from a standard target of a given element. The theoretical values of the Kα to Lα and Kβ to Lβ intensity ratios were calculated using theoretically tabulated values of shell/subshell photoionization cross sections, fluorescence yields, Coster-Kronig transition probabilities, and radiative decay rates for ηKLi≠ and ηKLi=0. The measured values are in good agreement with theoretical results. From Optika i Spektroskopiya, Vol. 97, No. 2, 2004, pp. 186–189. Original English Text Copyright ? 2004 by A. Kü?ük?nder, S?ğüt, E. Kü?ük?nder, Büyükkasap. This article was submitted by the authors in English.     

Crystal structure of nanostructured PbS films at temperatures of 293–423 K

The crystal structure of lead sulfide films prepared by the hydrochemical deposition has been studied by X-ray diffraction. The thickness of the films synthesized is ∼100 nm, the size of coherent scattering regions is ∼70 nm, and the value of microstrains is ∼0.20%. It is established, for the first time, that the as-synthesized PbS films and the same films annealed in the temperature range 293–423 K have a cubic crystal structure (space group Fm3m) different from the B1-type structure. In the crystal lattice of the structure revealed, sulfur atoms are located not only in the 4(b) positions but also in the 8(c) positions. The occupancies of the 4(b) and 8(c) positions by the S atoms are ∼0.84 and 0.08, respectively.     

Sublattices in crystals with low-symmetry systems

Complex crystals are represented by a set of identical or different Bravais sublattices. The presence of different Bravais sublattices in crystals results in the occurrence of latent symmetry manifested through their physical and physicochemical properties. The present paper studies the consistence of sublattices with different systems, including systems with higher symmetry, in monoclinic and triclinic crystals. Conditions of consistence following from the translational symmetry of different sublattices are found, and their spatial arrangement in crystals with the given systems is described. A relationship between the vectors of sublattice displacement from each other and systems of equivalent positions of space groups is obtained. It is demonstrated at what spatial arrangement of translatory less symmetric sublattices they can be combined into a translational sublattice with higher symmetry. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 55–62, April, 2007.     

Multidimensional crystal spaces with translation-compatible subspaces

The symmetry of the multidimensional crystal space R_(nk) which is a direct sum k of the n-dimensional crystal subspaces is investigated. The symmetry of the n-dimensional space constructed for the translation-compatible subspaces by embedding the k subspaces into each other is discussed. In the case of n = 3, the space R_(3k) describes the symmetry of a crystal with k sublattices corresponding to different Bravais types. A particular crystal structure is constructed by embedding the sublattices into each other with the corresponding spacing. As an illustration, the crystal spaces belonging to cubic syngony are considered. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 10–14, June, 2006.     

Phonon Spectrum and Structural Transformations at High Pressures in Vanadyl IV Phthalocyanine Crystals

The Raman scattering spectra and crystalline structure of vanadyl IV phthalocyanine (VOPc) at normal and high pressures has been studied. According to the X-ray diffraction data, the initial microcrystalline powder represented a mixture of the triclinic α phase (79%) and the monoclinic β phase (21%) possessing P$$\bar {1}$$ and P21/c symmetry, respectively. Raman spectra of the two phases are similar, but the phonon modes of the β phase are shifted toward higher frequencies (energies). The pressure dependence of the spectra of the α phase has been determined and it is established that the interval of 2.3–3.4 GPa reveals reversible pressure-dependent variations: above 3 GPa, some phonon modes exhibit splitting and the coefficients of pressure-induced (baric) shift for almost all modes show a decrease. A high-pressure feature observed in the Raman spectra can be related to changes in intermolecular interactions in crystalline structure of the α phase. The pressure dependence of the α phase unit cell volume measured at pressures increasing up to 4 GPa is a smooth monotonic function that can be well described by the Murnaghan equation of state. The obtained data were used to calculate the Grüneisen parameters of VOPc phonon modes.     

UV-induced synthesis,characterization and formation mechanism of silver nanoparticles in alkalic carboxymethylated chitosan solution

The silver nanoparticles (AgNPs) were synthesized in an alkalic aqueous solution of silver nitrate (AgNO₃)/carboxymethylated chitosan (CMCTS) with ultraviolet (UV) light irradiation. CMCTS, a water-soluble and biocompatible chitosan derivative, served simultaneously as a reducing agent for silver cation and a stabilizing agent for AgNPs in this method. UV–vis spectra and transmission electron microscopy (TEM) images analyses showed that the pH of AgNO₃/CMCTS aqueous solutions, the concentrations of AgNO₃ and CMCTS can affect on the size, amount of synthesized AgNPs. Further by polarized optical microscopy it was found that the CMCTS with a high molecular weight leads to a branch-like AgNPs/CMCTS composite morphology. The diameter range of the AgNPs was 2–8 nm and they can be dispersed stably in the alkalic CMCTS solution for more than 6 months. XRD pattern indicated that the AgNPs has cubic crystal structure. The spectra of laser photolysis of AgNO₃/CMCTS aqueous solutions identified the early reduction processes of silver cations (Ag⁺) by hydrated electron formed by photoionization of CMCTS. The rate constant of corresponding reduction reaction was 5.0 × 10⁹ M⁻¹ s⁻¹.     

Study of the surface structure of Si(1 1 1)-6 × 1(3 × 1)-Ag using X-ray crystal truncation rod scattering

The structure of the Si(1 1 1)-6 × 1-Ag surface is investigated using crystal truncation rod (CTR) scattering along 00 rod. For the measurement, we developed a manipulator suitable for observing CTR scattering at large momentum transfer perpendicular to the surface. The heights of the silver and reconstructed silicon atoms from the substrate were determined. We also compared the obtained positions with those of the Si(1 1 1)-√3 × √3-Ag surface and found that the heights of those reconstructed atoms are almost the same.     

Correlations in 11B NMR spectra of dihalo derivatives of bis(1,2-dicarbollyl)cobalt(III)

In the ¹¹B NMR spectra of dihalo derivatives of bis(dicarbollyl)cobalt(III), we have identified a correlation between the ¹¹B NMR chemical shifts of substituted boron atoms and boron atoms found in other positions on the carborane skeleton. We have observed an increased shielding effect for fluorine atoms (compared with other halogens), manifested in an upfield shift of the ¹¹B NMR signals for antipodal and trans boron atoms. For the fluorine-containing compound Bu₄N⁺ [8,8′-F₂-3,3′-Co(1,2-C₂B₉H₁₀)₂]⁻, we propose the following sequence of electron density transfer: B(8) → {B(6) and B(10)} → B(4, 7). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 547–549 (cont.), July–August, 2006.     

Thermodynamics and defect structures of silver sulfide

Published measurements of sulfur vapor pressure and silver electromotive force were used to determine thermodynamic properties of silver sulfide above 379 K. They were Gibbs-Duhem integrated to estimate the formation properties of stoichiometric Ag₂S of fcc, bcc, and monoclinic crystal structures. Statistical thermodynamics was applied to estimate free energies and find possible atom arrangements in off-stoichiometric silver sulfide. Theoretical calculations show that silver vacancies and atoms may be in quasi-chemical equilibrium between tetrahedral and octahedral sites in the fcc structure and between two states of atoms within tetrahedral sites in the bcc structure and within octahedral sites in the monoclinic structure. A strong indication is that vacancy clusters should predominate, each containing four-atom vacancies in the fcc phase and three-atom vacancies in the bcc phase.     

Photoionization spectra of silver atoms adsorbed on the surface of a ZnS single crystal

We have used photostimulated flash luminescence to study deep electronic states arising when silver ions Ag⁺ are deposited under high vacuum onto the surface of a ZnS single crystal, followed by creation of the conditions for neutralization of the silver ions. The flux density of the silver ion beam was 10⁷ cm⁻²·sec⁻¹. We have observed the appearance of two types of deep electronic states with photoionization energies 1.60 eV and 1.80 eV, arising after depositing the silver ions onto the surface of the ZnS single crystal. We have hypothesized that there may be two different preferred sites for adsorption of silver atoms on the zinc sulfide surface. The corresponding photoionization spectra of the adsorbed silver atoms have maxima at 775 nm and 690 nm. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 335–338, May–June, 2006.