Quantum chemical study of electronic and dynamic properties of metal and mixed non-stoichiometric clusters

The aim of this contribution is to show that quantum chemistry has suitable tools to extract the specific properties of small metallic and mixed non-stoichiometric clusters which cannot be obtained by extrapolation from the bulk properties to the atom. For this purpose, first the main features of the methods used for the calculations of the ground and excited states of clusters valid at zero temperature (T=0) will be sketched and the factors determining accuracy of results will be pointed out. The structural and optical response properties of cationic Na _n ⁺ clusters as a function of size will be presented and compared with experimental data. The series of non-stoichiometric alkali-halide clusters containing single and multiple excess electrons will serve as prototypes to study a possible “metal-insulator transition” and “segregation into metallic and ionic parts” in finite systems. Second, an outline of ab initio molecular dynamics methods based on gradient corrected density functional approach with gaussian basis used for determination of temperature dependent ground state properties will be presented. Different temperature behavior of distinct type of structures will be illustrated on an example of Li ₉ ⁺ cluster. Presented by V. Bonačić-Koutecky at the International Conference on “Atomic Nuclei and Metallic Clusters”, Prague, September 1–5, 1997. This work has been supported by the Deutsche Forschungsgemeinschaft (SFB 337, Energy transfer in molecular aggregates) and the Consiglio Nationale delle Ricerche (CNR, Rome).     

Solid polymer electrolytes based on squaric acid structure

Poly(squarate)s (PPS-1 and PPS-2) were synthesized by the reaction of squaryl dichloride with hydroquinone for PPS-1 and with 2,5-diethoxy-1,4-bis(trimethylsilyloxy)benzene for PPS-2, and the ionic conductivities, thermal properties, and electrochemical and thermal properties of their polymer electrolytes with LiN(CF₃SO₂)₂ were investigated. The ionic conductivity increased with increasing the lithium salt concentration for the PPS-1–LiN(CF₃SO₂)₂ electrolyte, and the highest ionic conductivities of 8.60 × 10⁻⁵ S/cm at 100 °C and 9.57 × 10⁻⁸ S/cm at 30 °C were found at the [Li] to [O] ratio of 2:1. And also, the ionic conductivity for the PPS-1–LiN(CF₃SO₂)₂ electrolyte increased with an increase in the lithium salt concentration, reached a maximum value at the [Li] to [O] ratio of 1:2, and then decreased. The highest ionic conductivity was to be 1.04 × 10⁻⁵ S/cm at 100 °C and 1.71 × 10⁻⁸ S/cm at 30 °C, respectively. Both polymer electrolytes exhibited relatively better electrochemical and thermal stabilities. Addition of the PPS-1 as a plasticizer into the poly(ethylene oxide) (PEO)–LiN(CF₃SO₂)₂ electrolyte system suppressed the crystallization of PEO, and improved the ionic conductivity at room temperature. Invited paper dedicated to Professor W. Weppner on his 65th birthday.     

Electrochemical study of P(VDF-HFP)/PMMA blended polymer electrolyte with high-temperature stability for polymer lithium secondary batteries

In the present study, a kind of solid polymer electrolyte (SPE) based on poly(vinylidene difluoride-co-hexafluoropropylene)/poly(methyl methacrylate) blends was prepared by a casting method to solve the safety problem of lithium secondary batteries. Owing to being plasticized with a room temperature ionic liquid, N-butyl-N′-methyl-imidiazolium hexafluorophosphate, the obtained SPE shows a thermal decomposition temperature over 300°C and an ionic conductivity close to 10⁻³ S cm⁻¹. The SPE-3 sample, in which the weight of two polymers is equivalent, possesses an ionic conductivity of 0.45 × 10⁻³ S cm⁻¹ at 25°C and presents an electrochemical window of 4.43 V. The ionic conductivity of the SPE-3 is as high as 1.73 × 10⁻³ S cm⁻¹ at 75°C approaching to that of liquid electrolyte. The electrochemical performances of the Li/LiFePO₄ cells confirmed its feasibility in lithium secondary batteries.     

Electric and dielectric properties of solution-gas interface grown amorphous AgCl films

Electric and dielectric properties of solution-gas interface grown AgCl thin film capacitors (Al/AgCl/Al) of various thicknesses have been studied in the frequency range 10¹–10⁶ Hz at various temperatures (303–393 K). I–V characteristics show ohmic, space-charge-limited, and thermionic emission conduction mechanisms to operate at low, intermediate and high voltages respectively. Capacitance decreases with increasing film thickness and applied frequency while it increases with increase of temperature. Loss factor (tanδ), which shows a pronounced minimum with frequency, increases with the rise of temperature and (tanδ)_min shifts to a higher frequency. The large values of capacitance and dielectric constant (ɛ) in the low frequency region indicate the possibility of an interfacial polarization mechanism to operate in this region while electronic and ionic polarizations dominate in the high frequency region.     

The Low-Temperature Expansion of the Wulff Crystal in the 3D Ising Model

We compute the expansion of the surface tension of the 3D random cluster model for q≥ 1 in the limit where p goes to 1. We also compute the asymptotic shape of a plane partition of n as n goes to ∞. This same shape determines the Wulff crystal to order o(ɛ) in the 3D Ising model (and more generally in the 3D random cluster model for q≥ 1) at temperature ɛ. Received: 15 February 2001/ Accepted: 11 May 2001     

Hydrogen in amorphous and crystalline ytterbium films

Ytterbium vapor condensation on a liquid-helium cooled substrate in a hydrogen atmosphere is used to obtain Yb-H films containing up to 55 at.% hydrogen. Various thermodynamic and kinetic parameters of the transition of these films from the amorphous to the crystalline state (a→c transition) are investigated along with the electrical conductivity of these states. It is shown that the investigated properties of Yb-H films containing up to 40 at.% hydrogen are essentially indistinguishable from those of pure Yb films in the temperature interval 4.2–293 K. Increasing the hydrogen concentration to 55 at.% leads to an insignificant increase in the electrical resistivity, the kinetic temperature, and the activation energy of the a→c transition, and also to a decrease of the propagation speed of self-maintaining avalanche (explosive) crystallization. Reasons for the observed influence of hydrogen on the properties of Yb-H films are analyzed. The examined low-temperature Yb-H condensates can be characterized as a “frozen” solid solution of hydrogen in ytterbium in the temperature interval 4.2–293 K. Storing such films at room temperature leads to the formation of ionic ytterbium dihydride YbH₂. Fiz. Tverd. Tela (St. Petersburg) 41, 177–182 (February 1999)     

Volumetric and transport properties of <Emphasis Type="Italic">N</Emphasis>-Butyl-<Emphasis Type="Italic">N</Emphasis>-methylpyrrolidinium bis(Trifluoromethanesulfonyl)imide–methanol binary mixtures

Densities, viscosities, and ionic conductivities were measured for the binary mixtures containing the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and methanol over the entire range of compositions at the temperature varying from 253.15 to 318.15 K. The densities and viscosities decrease monotonously with temperature and the content of ionic liquids (ILs). Furthermore, excess isobaric expansion coefficient has been calculated from the experimental densities. The dependence of temperature on the viscosity has been fitted to the Arrhenius law with high precision. The dependence of temperature on the ionic conductivity has also been gauged by both of the Arrhenius and Vogel–Tamman–Fulcher (VTF) equations. In fact, the shape of the curves shows that the temperature dependence of the conductivity does not follow a simple Arrhenius law, but a better fitting of experimental results is achieved using the VTF model. Additionally, the effects of ILs concentration on the viscosity and the conductivity have been examined using the Walden rule, which shows that the variation of conductivity is inversely proportional to viscosity. Excess molar volumes and viscosity deviations for all mixtures are evaluated and well fitted to the Redlich–Kister polynomial expansions. Physicochemical properties show two clearly distinguished behaviors corresponding to ILs-rich and methanol-rich regions, with distinct transport and volumetric properties. The obtained results are discussed in terms of dipolar interactions and hydrogen bonding establishment between ions of ILs and the methanol molecules.     

Magnetic and electrical properties of cation-substituted sulfides MexMn1 ? xS (Me = Co, Gd)

The temperature dependences of the specific magnetization σ and the electrical resistivity ρ of Me _x Mn_{1 − x} S single crystals (Me= Co, Gd; x= 0.05) have been studied in the temperature range 80 K < T < 1000 K. The samples under study have revealed the presence of a spontaneous magnetic moment below the Néel temperature (T _N) and ferromagnetic clusters in Gd_0.05Mn_0.95S in the temperature range 146 K < T < 680 K. Substitution of gadolinium for manganese initiates a transition from p-type to n-type conduction. The change in the conduction type is accompanied by an increase in the electrical resistivity at 300 K by approximately one order of magnitude and, accordingly, by a decrease in the activation energy. The magnetic and electrical properties of the crystals under study have been interpreted in terms of the cluster model with temperature-dependent ferromagnetic exchange and an electron localized in this cluster. Original Russian Text ? S.S. Aplesnin, L.I. Ryabinkina, O.B. Romanova, V.V. Sokolov, A.Yu. Pichugin, A.I. Galyas, O.F. Demidenko, G.I. Makovetskiĭ, K.I. Yanushkevich, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 4, pp. 661–664.     

Critical evolution of the local order parameters related to the nanopolar domains in Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramics

In the present paper, Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics prepared by the columbite method were investigated. The dielectric study indicates typical relaxor properties, with a frequency dispersion in the range of 200–350 K. The relaxor-to-paraelectric phase transition was evidenced by the continuous decrease of the local order parameter derived from the permittivity-temperature data. As a result of the critical behavior, the main Raman modes show anomalies at: (i) ∼150 K; (ii) ∼220 K (i.e. close to the critical temperature reported for the field-induced ferroelectric state in PMN single crystal); (iii) ∼260 K (i.e. the temperature of the permittivity maximum); (iv) ∼350 K (the temperature for initiation of the cluster freezing process T ^*); (v) ∼620 K (Burns temperature). The frequency split of the doublet at ∼605 and ∼500 cm⁻¹ presents a critical behavior related to the local symmetry lowering and to the structure ordering due to a phase transformation which takes place below T ^*. The tunability in the paraelectric state was interpreted in terms of reorientation of the non-interacting nanopolar clusters in a double-well potential. The temperature dependence of the nanopolar domain size also shows anomalies in the range of T ^*. The size and dynamics of the polar nanodomains is essential in determining the functional properties of the Pb(Mg_1/3Nb_2/3)O₃ relaxor.     

Structural and electrical characterisation of strontium zirconate proton conductor co-sputter deposited coatings

SrZr_1−x Y _x O₃ coatings were co-sputtered from metallic Zr–Y (84–16 at.%) and Sr targets in the presence of a reactive argon–oxygen gas mixture. The structural and chemical features of the film have been assessed by X-ray diffraction and scanning electron microscopy. The electrical properties have been investigated for different substrates by Complex Impedance Spectroscopy as a function of crystalline state, temperature and atmosphere. The as-deposited coatings are amorphous and crystallise after annealing at 673 K for 2 h under air. The stabilisation of the perovskite structure is a function of the nominal composition. The films are dense and present a good adhesion on different substrates. Crystallisation and mechanical stresses are detected by alternating current (AC) impedance spectroscopy. Significant ionic conductivity in the 473–823 K temperature range is evidenced in air. Two different conduction regimes in the presence of steam are attributed to a modification of the charge carrier nature. In spite of low conductivity values (σ ~10⁻⁶ S.cm⁻¹ at 881 K), the activation energies are in agreement with that of Y-doped strontium zirconate ceramics (~0.7 eV in air).     

Cluster structure of oriented polyethylene terephthalate films

The surface of polyethylene terephthalate films (the degree of crystallinity is 0.12–0.18) subjected to uniaxial drawing near the glass transition temperature of 353 K has been studied by electron microscopy and IR spectroscopy. Formation of a percolation cluster of densely packed particles, which is deformed as a whole entity, has been revealed in the films. The volume fraction of the cluster (Ω ≈ 0.5) and the degree of chain unfolding (β ≈ 0.7) at 343 K are independent of the drawing ratio in the region 1.1 ≤ λ ≤ 3.0. Near λ = 2.5, plane orientation of chains, for which the radius of particles in the amorphous phase is close to the radius of unperturbed coil, has been found. At 363 K, the cluster framework formation (Ω ≈ 0.6 and β ≈ 1) terminates near λ = 2.5. The drawing ratio λ ≥ 4 corresponds to microfibrils of chains with the parameters Ω ≈ 0.15 and β ≈ 1 and the fractal dimensionality D ≈ 1.     

Studies on PEO-based sodium ion conducting composite polymer films

A sodium ion conducting composite polymer electrolyte (CPE) prepared by solution-caste technique by dispersion of an electrochemically inert ceramic filler (SnO₂) in the PEO–salt complex matrix is reported. The effect of filler concentration on morphological, electrical, electrochemical, and mechanical stability of the CPE films has been investigated and analyzed. Composite nature of the films has been confirmed from X-ray diffraction and scanning electron microscopy patterns. Room temperature d.c. conductivity observed as a function of filler concentration indicates an enhancement (maximum) at 1–2 wt% filler concentration followed by another maximum at ∼10 wt% SnO₂. This two-maxima feature of electrical conductivity as a function of filler concentration remains unaltered in the CPE films even at 100 °C (i.e., after crystalline melting), suggesting an active role of the filler particles in governing electrical transport. Substantial enhancement in the voltage stability and mechanical properties of the CPE films has been noticed on filler dispersion. The composite polymer films have been observed to be predominantly ionic in nature with t _ion ∼ 0.99 for 1–2 wt% SnO₂. However, this value gets lowered on increasing addition of SnO₂ with t _ion ∼ 0.90 for 25 wt% SnO₂. A calculation of ionic and electronic conductivity for 25 wt% of SnO₂ film works out to be ∼2.34 × 10⁻⁶ and 2.6 × 10⁻⁷ S/cm, respectively.     

Non-coexistence of Infinite Clusters in Two-Dimensional Dependent Site Percolation

This paper presents three results on dependent site percolation on the square lattice. First, there exists no positively associated probability measure on {0,1}^{\mathbb Z2}\{0,1\}^{\mathbb {Z}^{2}} with the following properties: (a) a single infinite 0cluster exists almost surely, (b) at most one infinite 1∗cluster exists almost surely, (c) certain probabilities regarding 1∗clusters are bounded away from zero. Second, the coexistence of an infinite 1∗cluster and an infinite 0cluster has probability zero when the underlying probability measure is ergodic with respect to translations, positively associated, and satisfies the finite energy condition. The third result analyzes the typical structure of infinite clusters of both types in the absence of positive association. Namely, under a slightly sharpened finite energy condition, the existence of infinitely many disjoint infinite self-avoiding 1∗paths follows from the existence of an infinite 1∗cluster. The same holds with respect to 0paths and 0clusters.     

AC Conductivity,XRD and transport properties of melt quenched PbI<Subscript>2</Subscript>–Ag<Subscript>2</Subscript>O–Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Composite materials used for electrode and electrolyte materials have been intensely studied in view of their advantages such as higher conductivity and better operational performance compared to their single-phase counterparts. The present work aims at studying the electrical and structural characteristics of a new composite electrolyte namely, (PbI₂) _x  − (Ag₂O–Cr₂O₃)_100−x where x = 5, 10, 15, 20, and 25 mol%, respectively, prepared by the melt quenching technique. The room temperature X-ray diffraction spectra revealed certain crystalline phases in the samples. AC conductivity analysis for all the prepared samples was carried out over the frequency range 1 MHz–20 Hz and in the temperature window 297–468 K. The room temperature conductivity values were calculated to be in the order of 10⁻⁵–10⁻³ Scm⁻¹. An Arrhenius dependence of temperature with conductivity was observed, and the activation energies calculated were found to be in the range 0.27–0.31 eV. Furthermore, the total ionic transport number (t _i) values obtained for all these indicated the ionic nature of this system. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Synthesis, crystal structure, thermal and dielectric properties of bis(p-phenylenediammonium) chloride hexachlorobismuthate(III) monohydrate [C6H4(NH3)2]2ClBiCl6.H2O

Synthesis, crystal structure, and dielectric properties of [C₆H₄(NH₃)₂]₂ClBiCl₆.H₂O are reported. The compound crystallizes in the monoclinic system with space group P2₁/n. The unit cell dimensions are a = 9.836(5), b = 19.582(5), c = 13.082(5) ?, β = 104.731(5)° with Z = 4. The atomic arrangement can be described by an alternation of organic and inorganic layers. The anionic layer is built up of octahedral of [BiCl₆]^3- arranged in sandwich between the organic layers. The crystal packing is governed by means of the ionic N–H···Cl hydrogen bonds, forming a three-dimensional network. The dielectric properties have been investigated at temperature range from 297 to 410 K at various frequencies (10 Hz–100 kHz). Dielectric studies were performed to confirm results obtained with thermal analysis. The evolution of dielectric constant as a function of temperature and frequency of single crystal has been investigated in order to determine some related parameters.     

Application of ionic liquid doped solid polymer electrolyte

The electrical, structural, and photoelectrochemical properties of the polymer electrolyte PEO:NaI/I₂ doped with an ionic liquid 1-ethyl 3-methylimidazolium dicyanamide (EMImDCN) have been reported. Incorporation of the ionic liquid (IL) increases the membrane homogeneity, decreased surface roughness, and enhances the short current (J _sc). Additionally, the doping of IL provides more charge carriers which enhances overall ionic conductivity (σ). The optimized σ was found at 40 wt.% IL composition. The fabricated DSSC using this new solid electrolyte showed 1.43% efficiency at 100 mW cm⁻².     

Fifty years of Szigeti’s dielectric theory — A review

During the period 1949–1961 Szigeti published four seminal papers on the dielectric behaviour of crystals. Szigeti’s theory is applicable to isotropic and anisotropic, ionic and covalent crystals with different structures. Szigeti’s theory connects dielectric, spectroscopic and elastic properties. An important outcome of Szigeti’s theory is the concept of the effective ionic charge (s). It is pointed out that s correlates with a number of physical properties and is a measure of ionicity of the interatomic bond. Since Szigeti’s work, several theoretical models have been proposed to account for the fact that s < 1. These models provide an insight into the complex polarization mechanisms in solids. This review summarizes Szigeti’s work and the work that followed; the implications and applications of Szigeti’s theory are discussed. Some new results are also included. Dedicated to the memory of late Prof. P S Narayanan.     

Melting temperature variation with concentration of alkali halides in mixed crystal systems

Diffusion-vibration theory of melting (Sharmaet al 1991) has been extended to study the variation in the melting temperature of mixed ionic crystals with concentration. The melting temperature varies non-linearly with concentration in the KCl _x Br_1−x , RbCl _x Br_1−x , K _x Rb_1−x Br and NaCl _x Br_1−x mixed alkali halides and shows a sharp increase in melting temperature for values ofx>0.5 which is in good agreement with the experimental values. This behaviour has been explained on the basis of present propounded theory.     

Thermal hysteresis of the permittivity of Li0.12Na0.88TayNb1?yO3 solid solutions (y ≥ 0.7) prepared under high or normal pressure

The structural characteristics and dielectric properties (ε′, tanδ) of Li_0.12Na_0.88Ta_yNb_1−y O₃ solid solutions (y ≥ 0.7) synthesized under high or normal pressure (HP and NP ceramics, respectively) were studied. It was established that these solid solutions have an orthorhombic perovskite structure (space group Pnma) in the paraelectric state. The temperature and frequency dependences of the dielectric properties of the solid solutions are described in terms of microinhomogeneity of a system containing ferroelectric clusters with an enhanced Nb content as compared to that in the matrix. The characteristics of the cluster system depend on the method by which the ceramics were prepared. The HP ceramic is more homogeneous on the microscale. The permittivity ε′ was found to undergo thermal hysteresis in the region from 200 to 400 K, the parameters of which strongly differ for the HP and NP ceramics. The temperature of the maximum ε′ obtained in cooling runs for the NP and HP ceramics is 50–60 and 110 K lower, respectively, than that on the heating branch. The hysteresis may originate from interaction of the antipolar mode condensing under cooling with nonpolar ordered distortions, which drives the system to the state of global minimum. When the system residing in this state is heated, this mode undergoes decondensation at a higher temperature. __________ Translated from Fizika Tverdogo Tela, Vol. 47, No. 4, 2005, pp. 679–685. Original Russian Text Copyright ? 2005 by Olekhnovich, Radyush, Vyshatko, Moroz, Pushkarev, Palatnikov.     

Conductivity studies of plasticized anhydrous PEO-KOH alkaline solid polymer electrolyte

Polyethylene oxide (PEO)–potassium hydroxide (KOH)-based alkaline solid polymer electrolyte films have been prepared by using methanol as solvent. The highest room temperature ionic conductivity of (2.1 ± 0.5) × 10⁻⁸ S cm⁻¹ was achieved for the composition of 70 wt% PEO:30 wt% KOH. The addition of plasticizer, ethylene carbonate, propylene carbonate, or polyethylene glycol to the highest conductivity of PEO–KOH system helps to increase the ambient ionic conductivity to the order of 10⁻⁶–10⁻⁴ S cm⁻¹. The log σ vs 1/T plot of PEO–KOH showed a small conductivity decrease at 50–60 °C range. The small decrease and the hysteresis that occur during the heating–cooling cycle was overcome by the presence of the plasticizer. X-ray diffraction observation supports the conductivity results.