Ultrafast electron-induced desorption of water from nanometer amorphous solid water films

Laser-induced desorption of water molecules from nanometer amorphous solid water films supported on a single-crystal platinum substrate is reported. A femtosecond laser pulse creates hot substrate electrons, which are injected into the water layer, resulting in significant desorption at the water-vacuum interface. The dependence of the desorption yield on film thickness and results for isotopic spacer and capping layers reveal that the desorbing water originates from relatively deep down into the water layer, i.e., from several nanometers below the surface. This is proposed to be the result of cooperative electronic effects resulting from the high electron densities in the thin water film, which cause a transient destabilization of the water H-bonded network. Motion of excited water molecules through the layer is enabled by mixing within the layer on ultrafast timescales during the desorption process.     

Analysis of the photon–photon resonance influence on the direct modulation bandwidth of dual-longitudinal-mode distributed feedback lasers

The paper explores the possibilities to extend the direct modulation bandwidth in dual-longitudinal-mode distributed feedback lasers by exploiting the photon–photon resonance induced by the interaction of the two modes in the laser cavity. The effects on the direct amplitude modulation and on the direct modulation of the difference frequency between the two modes are analyzed using simulation and experimental results. When the photon–photon resonance, which occurs at the difference frequency between the two modes, is properly placed at a higher frequency than the carrier-photon resonance, the small-signal amplitude modulation (AM) bandwidth of the laser can be significantly increased. However, both simulations and experiments point out that a high small-signal AM bandwidth does not lead to a high large-signal AM bandwidth if the small-signal modulation response has significant variations across the modulation bandwidth. The paper shows that a high large-signal AM bandwidth is obtained when the two modes are significantly unbalanced, whereas a high-bandwidth difference frequency modulation can be best detected when the two modes are balanced and the DC bias is properly chosen.     

On the Fourier spectrum of symmetric Boolean functions

We study the following questionWhat is the smallest t such that every symmetric boolean function on κ variables (which is not a constant or a parity function), has a non-zero Fourier coefficient of order at least 1 and at most t?We exclude the constant functions for which there is no such t and the parity functions for which t has to be κ. Let τ (κ) be the smallest such t. Our main result is that for large κ, τ (κ)≤4κ/logκ.The motivation for our work is to understand the complexity of learning symmetric juntas. A κ-junta is a boolean function of n variables that depends only on an unknown subset of κ variables. A symmetric κ-junta is a junta that is symmetric in the variables it depends on. Our result implies an algorithm to learn the class of symmetric κ-juntas, in the uniform PAC learning model, in time n ^o(κ) . This improves on a result of Mossel, O’Donnell and Servedio in [16], who show that symmetric κ-juntas can be learned in time n ^2κ/3.     

Encapsulation of cyanometalates by a tris-macrocyclic ligand tricopper(II) complex: syntheses, structural variation, and magnetic exchange coupling pathways

The reaction of [M(CN)(6)](3-) (M = Cr(3+), Mn(3+), Fe(3+), Co(3+)) and [M(CN)(8)](4-/3-) (M = Mo(4+/5+), W(4+/5+)) with the trinuclear copper(II) complex of 1,3,5-triazine-2,4,6-triyltris[3-(1,3,5,8,12-pentaazacyclotetradecane)] ([Cu(3)(L)](6+)) leads to partially encapsulated cyanometalates. With hexacyanometalate(III) complexes, [Cu(3)(L)](6+) forms the isostructural host-guest complexes [[[Cu(3)(L)(OH(2))(2)][M(CN)(6)](2)][M(CN)(6)]][M(CN)(6)]30 H(2)O with one bridging, two partially encapsulated, and one isolated [M(CN)(6)](3-) unit. The octacyanometalates of Mo(4+/5+) and W(4+/5+) are encapsulated by two tris-macrocyclic host units. Due to the stability of the +IV oxidation state of Mo and W, only assemblies with [M(CN)(8)](4-) were obtained. The Mo(4+) and W(4+) complexes were crystallized in two different structural forms: [[Cu(3)(L)(OH(2))](2)[Mo(CN)(8)]](NO(3))(8)15 H(2)O with a structural motif that involves isolated spherical [[Cu(3)(L)(OH(2))](2)[M(CN)(8)]](8+) ions and a "string-of-pearls" type of structure [[[Cu(3)(L)](2)[M(CN)(8)]][M(CN)(8)]](NO(3))(4) 20 H(2)O, with [M(CN)(8)](4-) ions that bridge the encapsulated octacyanometalates in a two-dimensional network. The magnetic exchange coupling between the various paramagnetic centers is characterized by temperature-dependent magnetic susceptibility and field-dependent magnetization data. Exchange between the CuCu pairs in the [Cu(3)(L)](6+) "ligand" is weakly antiferromagnetic. Ferromagnetic interactions are observed in the cyanometalate assemblies with Cr(3+), exchange coupling of Mn(3+) and Fe(3+) is very small, and the octacoordinate Mo(4+) and W(4+) systems have a closed-shell ground state.     

Tuning of inter- versus intrachain magnetic interactions in cyano-bridged Ni(II)/M(III) (M = Cr, Fe, Co) chain complexes

The reaction of [M(CN)6]3- (M = Cr3+, Fe3+, Co3+) with the nickel(II) complex of 2,4-diamino-1,3,5-triazin-6-yl-{3-(1,3,5,8,12-pentaazacyclotetradecane)} ([NiL]2+) in excess of ANO3 or ACl (A = Li+, Na+, K+, Rb+, Cs+, NH4+) leads to the cyano-bridged dinuclear assemblies A{[NiL][M(CN)6]}.xH2O (x = 2-5). X-ray structures of Li{[NiL][Cr(CN)6]}.5H2O, NH4{[NiL][Cr(CN)6]}.3.5H2O, K{[NiL][Cr(CN)6]}.4H2O, K{[NiL][Fe(CN)6]}.4H2O, Rb{[NiL][Fe(CN)6]}.3.5H2O, and Cs{[NiL][Fe(CN)6]}.3.5H2O, as well as the powder diffractometry of the entire Fe(III) series, are reported. The magnetic properties of the assemblies are dependent on the monocation A and discussed in detail. New efficient pathways for ferromagnetic exchange between Ni(II) and Fe(III) or Cr(III) are demonstrated. Field dependencies of the magnetization for the Fe(III) samples at low temperature and low magnetic field indicate a weak interchain antiferromagnetic coupling, which is switched to ferromagnetic coupling at increasing magnetic field (metamagnetic behavior). The interchain magnetic coupling can be tuned by the size of the A cations.     

Photocatalytic properties of Ta-doped TiO2

Ionics - This work reports the effect of tantalum (0.1–1 at.% Ta) on the photocatalytic performance of TiO2 annealed at 1373 and 1673 K in air. It was shown that addition of...     

Structural characteristics of olivine Li(Mg0.5Ni0.5)PO4 via TEM analysis

The structural characteristics of olivine-type lithium orthophosphate Li(Mg_0.5Ni_0.5)PO₄ synthesized via solid-state reaction have been studied using X-ray diffraction, ion beam technique, scanning electron microscopy, infrared spectroscopy, transmission electron microscopy and energy dispersive X-ray analysis. The parent LiNiPO₄ compound can be synthesized in olivine structure without any evidence of secondary phases as impurities. The structural quality of the parent LiNiPO₄ in the absence of secondary component phases resulted in the formation of hexagonal closed packed structure. The olivine analogue compound containing mixed M (M?=?Mg, Ni) cations, Li(Mg_0.5Ni_0.5)PO₄ contained Li₃PO₄ as a second phase upon synthesis, however a carbothermal reduction method produced a single-phase compound. The redox behaviour of carbon-coated Li(Mg_0.5Ni_0.5)PO₄ cathode in aqueous lithium hydroxide as the electrolyte showed reversible lithium intercalation.     

Lipscomb’s L(A) Space Fractalized in l p (A)

In this paper, by using some of our new results concerning the shift space for an infinite IFS (see A. Mihail and R. Miculescu, The shift space for an infinite iterated function system, Math. Rep. Bucur. 11 (2009), 21?C32), we show that, for an infinite set A, the embedded version of the Lipscomb space L(A) in l ^p (A), ${p \in [1,\infty)}$ , with the metric induced from l ^p (A), denoted by ${\omega_p^A}$ , is the attractor of an infinite iterated function system comprising affine transformations of l ^p (A). In this way we provide a generalization of the positive answer that we gave to an open problem of J.C. Perry (see Lipscomb??s universal space is the attractor of an infinite iterated function system, Proc. Amer. Math. Soc. 124 (1996), 2479?C2489) in one of our previous works (see R. Miculescu and A. Mihail, Lipscomb space ?? ^A is the attractor of an infinite IFS containing affine transformations of l ²(A), Proc. Amer. Math. Soc. 136 (2008), 587?C592). Moreover, as a byproduct, we provide a generalization of Corollary 15 from Perry??s paper by proving that ${\omega_p^A}$ is a closed subset of l ^p (A).     

Linear and Nonlinear Viscoelasticity of a Model Unentangled Polymer Melt: Molecular Dynamics and Rouse Modes Analysis

Summary: Using molecular dynamics simulations, we determine the linear and nonlinear viscoelastic properties of a model polymer melt in the unentangled regime. Several approaches are compared for the computation of linear moduli and viscosity, including Green‐Kubo and nonequilibrium molecular dynamics (NEMD). An alternative approach, based on the use of the Rouse modes, is also discussed. This approach could be used to assess local viscoelastic properties in inhomogeneous systems. We also focus on the contributions of different interactions to the viscoelastic moduli and explain the microscopic mechanisms involved in the mechanical response of the melt to external solicitation.