A symmetry-adapted method for the determination of the lattice energy and properties of ionic crystals

An efficient symmetry-adapted algorithm is described for the calculation of the elastic and dielectric properties of perfect ionic crystals.     

Solvation dynamics in methanol: Experimental and molecular dynamics simulation studies

We have investigated the ultrafast dynamics of methanol by time dependent fluorescent shift experiments and molecular dynamic simulations. The experiments were performed with two different probe molecules, 1-aminonaphthalene and coumarin 153. The molecular dynamic simulations employed these probes as well as small atomic and diatomic solutes. We find a previously unobserved fast decay component in the solvation response of methanol. The molecular dynamics results are in good agreement with this experimental result. The origin of this fast response and the linearity of the solvent response are discussed.     

On an integral method for backward boundary layers

Zusammenfassung Eine Integralmethode für die Lösung von zweidimensionalen Grenzschichtgleichungen wird entwickelt für Fälle, in denen die Lösungen sich anfänglich wie diejenigen von End-Grenzschichten benehmen. Diese Lösungen sind von Goldstein behandelt worden. Die bedeutendste Anwendung betrifft den Fall, wo ein zweidimensionaler Strom gegen eine Öffnung fliesst, durch welche die Flüssigkeit entleert wird. In erster Annäherung wird die Grenzschichtströmung für grosse Entfernungen von der Öffnung durch die Ähnlichkeitsgesetze der konvergenten Strömung in einem keilförmigen Kanal beschrieben. Um Strömungen dieser Art zu studieren, die über lange Entfernungen laufen, wird die Geschwindigkeit am Rande der Grenzschicht an Stelle der Entfernung längs der Grenzschicht als unabhängige Veränderliche eingeführt. Die beschriebene Methode wird auf den Fall der Strömung in Richtung eines Schlitzes angewendet, ausgehend von einem unendlichen Halbraum, ferner auf den Fall einer Strömung um eine endliche Platte, die senkrecht zur Strömungsrichtung steht. In beiden Beispielen ist die Potentialströmung in der Form des Kirchhoff-Rayleighschen Gesetzes angenommen, wobei die freien Stromlinien an die scharfen Kanten gebunden sind. Die Methode wird verallgemeinert, so dass sie für allgemeinere End-Grenzschichten benutzt werden kann. Die Resultate stimmen ausgezeichnet mit denen der Methode von Thwaites sowie mit den Ähnlichkeitslösungen von Falkner-Skan überein.     

Finite time blowup of the <Emphasis Type="Italic">n</Emphasis>-harmonic flow on <Emphasis Type="Italic">n</Emphasis>-manifolds

In this paper, we generalize the no-neck result of Qing and Tian (in Commun Pure Appl Math 50:295–310, 1997) to show that there is no neck during blowing up for the n-harmonic flow as \(t\rightarrow \infty \). As an application of the no-neck result, we settle a conjecture of Hungerbühler (in Ann Scuola Norm Sup Pisa Cl Sci 4:593–631, 1997) by constructing an example to show that the n-harmonic map flow on an n-dimensional Riemannian manifold blows up in finite time for \(n\ge 3\).     

Electrochemical and Spectroscopic Properties of Fly Ash–Polyaniline Matrix Nanorod Composites

Polyaniline (PANI) nanocomposites were prepared with fly ash (FA) either by aging the starting materials (aniline and FA) before oxidative polymerisation or by including poly(styrene sulphonic acid) (PSSA) eliminating the aging step. The aging procedure formed polymer nanotubes that have cross-sectional diameters of 50–110 nm. The procedure involving PSSA produced nanorods and nanofibres composites that have diameters of 100–500 nm and length of up to 10 μm attributed to the presence of metal oxides and silica in FA. The electrochemical analysis of the PANI–PSSA–FA nanorod composites shows three redox couples with formal potentials, , values of 105 mV, 455 mV and 670 mV, and conductance, C, value of 1.21 × 10⁻² S. The UV-Vis spectroscopy of the polymeric nanorod shows absorption maxima at 340 and 370 nm (due to π–π^* transition of the benzoid rings), and 600–650 nm (due to charge transfer excitons of the quinoid structure), which are characteristic of emeraldine base.     

Influence of Process Parameters on the Reaction Kinetics of the Chromium‐Catalyzed Trimerization of Ethylene

In this paper we report the results of an extensive experimental kinetic study carried out on the novel ethylene trimerization catalyst system, comprising the chromium source [CrCl₃(thf)₃] (thf=tetrahydrofuran), a Ph₂P‐N(iPr)‐P(Ph)‐N(iPr)H (PNPNH) ligand (Ph=phenyl, iPr=isopropyl), and triethylaluminum (AlEt₃) as activator. It could be shown that the initial activity shows a first‐order dependency on the ethylene concentration. Also, a first‐order dependency was found for the catalyst concentration. The initial activity follows a typical Arrhenius behavior with an experimentally determined activation energy of 52.6 kJ mol^?1. At elevated temperatures (ca. 80 °C), a significant deactivation was observed, which can be tentatively traced back to a ligand rearrangement in the presence of AlEt₃. After a fast initial phase, a pronounced ‘kink’ in the ethylene‐uptake curve is observed, followed by a slow, almost linear, further increase of the total ethylene consumption. The catalyst composition, in particular the ligand/chromium and the cocatalyst/chromium molar ratio, has a strong impact on the catalytic performance of the trimerization of ethylene.     

Elemental distribution and thermoelectric properties of layered tellurides 39R-M(0.067)Sb(0.667)Te(0.266) (M=Ge, Sn)

The isostructural phases 39R‐Ge_0.067Sb_0.667Te_0.266 (R$\bar 3The isostructural phases 39R-Ge(0.067)Sb(0.667)Te(0.266) (R3m, a=4.2649(1), c=75.061(2) ?) and 39R-Sn(0.067)Sb(0.667)Te(0.266) (R3m, a=4.2959(1), c=75.392(2) ?) were prepared by quenching stoichiometric melts of the pure elements and subsequent annealing at moderate temperatures. Their structures are comparable to "superlattices" synthesized by layer-by-layer deposition onto a substrate. These structures show no stacking disorder by electron microscopy. The structure of the metastable layered phases are similar to that of 39R-Sb(10)Te(3) (equivalent to Sb(0.769)Te(0.231)), which contains four A7 gray-arsenic-type layers of antimony alternating with Sb(2)Te(3) slabs. Joint refinements on single-crystal diffraction data using synchrotron radiation at several K edges were performed to enhance the scattering contrast. These refinements show that the elemental distributions at some atom positions are disordered whereas otherwise the structures are long-range ordered. The variation of the elemental concentration correlates with the variation in interatomic distance. Z-contrast scanning transmission electron microscopy (HAADF-STEM) on 39R-Ge(0.067)Sb(0.667)Te(0.266) confirms the presence of concentration gradients. The carrier-type of the isostructural metal (A7-type lamellae)-semiconductor heterostructures (Ge/Sn-doped Sb(2)Te(3) slabs) varies from n-type (Ge(0.067)Sb(0.667)Te(0.266)) to p-type (Sn(0.067)Sb(0.667)Te(0.266)). Although the absolute values of the Seebeck coefficient reached about 50-70 μV/K and the electrical conductivity is relatively high, the two isotypic phases exhibit a maximal thermoelectric figure of merit (ZT) of 0.06 at 400 °C as their thermal conductivity (κ≈8-9.5 W/mK at 400 °C) lies interestingly in between that of antimony and pure Sb(2)Te(3).     

Single-ion heat capacities, C(p)(298)ion, of solids: with a novel route to heat-capacity estimation of complex anions

Single-ion heat capacities, C(p)(298)(ion), are additive values for the estimation of room-temperature (298 K) heat capacities of ionic solids. They may be used for inferring the heat capacities of ionic solids for which values are unavailable and for checking reported values, thus complementing our independent method of estimation from formula unit volumes (termed volume-based thermodynamics, VBT). Analysis of the reported heat-capacity data presented here provides a new self-consistent set of heat capacities for both cations and anions that is compatible (and thus may be combined) with an extensive set developed by Spencer. The addition of a large range of silicate species permits the estimation of the heat capacities of many silicate minerals. The single-ion heat capacities of individual silicate anions are observed to be strictly proportional to the total number of atoms (Si plus O), n, contained within the silicate anion complex itself (e.g., for the anion Si(2)O(7)(2-), n = 9, for SiO(4)(2-), n = 5), C(p)(silicate anion)/J K(-1) mol(-1) = 13.8n, in a new rule that is an extension of the Neumann-Kopp relationship. The same linear relationship applies to other homologous anion series (for example, oxygenated heavy-metal anion complexes such as niobates, bismuthates, and tantalates), although with a different proportionality constant. A similar proportionality, C(p)(complex anion)/J K(-1) mol(-1) ≈ 17.5n, which may be regarded as a convenient "rule of thumb", also applies, although less strictly, to complex anions in general. The proportionality constants reflect the rigidity of the complex anion, being always less than the Dulong-Petit value of 25 J K(-1) mol(-1). An emergent feature of our VBT and single-ion approaches to an estimation of the thermodynamic properties is the identification of anomalies in measured values, as is illustrated in this paper.