Concerted and stepwise proton-coupled electron transfers in aquo/hydroxo complex couples in water: oxidative electrochemistry of [Os(II)(bpy)(2)(py)(OH(2))](2+)

Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.     

Transversal and Longitudinal Gluon Spectral Functions from Twisted Mass Lattice QCD with <Emphasis Type="Italic">N</Emphasis><Subscript><Emphasis Type="Italic">f</Emphasis></Subscript> = 2 + 1 + 1 Flavors

I report on the first application of a novel, generalized Bayesian reconstruction (BR) method for spectral functions to the characterization of QCD constituents. These spectral functions find applications in off-shell kinetics of the quark-gluon plasma and in calculations of transport coefficients. The new BR method is applied to Euclidean propagator data, obtained in Landau gauge on lattices with N_f = 2 + 1 + 1 dynamical flavors by the “twisted mass at finite temperature” (tmfT) collaboration. The deployed reconstruction method is designed for spectral functions that can exhibit positivity violation (opposed to that of hadronic bound states). The transversal and longitudinal gluon spectral functions show a robust structure composed of quasiparticle peak and a negative trough. Characteristic differences between the hadronic and the plasma phase and between the two channels become visible. We obtain the temperature dependence of the transversal and longitudinal gluon masses.     

Fire retardancy mechanisms of arylphosphates in polycarbonate (PC) and PC/acrylonitrile-butadiene-styrene

The pyrolysis of polycarbonate (PC) and PC/acrylonitrile-butadiene-styrene (PC/ABS) with and without arylphosphates (triphenylphosphate TPP, resorcinol-bis(diphenyl phosphate) RDP and bisphenol A bis(diphenyl phosphate) BDP) is investigated by thermal analysis as key to understanding the flame retardancy mechanisms and corresponding structure–property relationships. The correspondence between the decomposition temperature range of arylphosphates and PC is pointed out as prerequisite for the occurrence of the reaction between arylphosphate and structures that are typical for the beginning of PC decomposition. Resulting cross-linking enhances charring in the condensed phase and competes with the alternative release of phosphate in the gas phase and thus flame inhibition. Flame inhibition was identified as the main flame retardancy mechanism. The additional condensed phase mechanisms optimise the performance.     

On the nature of the phase transition in <Emphasis Type="Italic">SU</Emphasis>(<Emphasis Type="Italic">N</Emphasis>), <Emphasis Type="Italic">Sp</Emphasis>(2) and <Emphasis Type="Italic">E</Emphasis>(7) Yang–Mills theory

We study the nature of the confinement phase transition in d=3+1 dimensions in various non-abelian gauge theories with the approach put forward in Phys. Lett. B 684, 262 (2010). We compute an order-parameter potential associated with the Polyakov loop from the knowledge of full 2-point correlation functions. For SU(N) with N=3,…,12 and Sp(2) we find a first-order phase transition in agreement with general expectations. Moreover our study suggests that the phase transition in E(7) Yang–Mills theory also is of first order. We find that it is weaker than for SU(N). We show that this can be understood in terms of the eigenvalue distribution of the order parameter potential close to the phase transition.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

Error estimates and specification parameters for functional renormalization

We present a strategy for estimating the error of truncated functional flow equations. While the basic functional renormalization group equation is exact, approximated solutions by means of truncations do not only depend on the choice of the retained information, but also on the precise definition of the truncation. Therefore, results depend on specification parameters that can be used to quantify the error of a given truncation. We demonstrate this for the BCS–BEC crossover in ultracold atoms. Within a simple truncation the precise definition of the frequency dependence of the truncated propagator affects the results, indicating a shortcoming of the choice of a frequency independent cutoff function.     

Large volume behaviour of Yang-Mills propagators

We investigate finite volume effects in the propagators of Landau gauge Yang-Mills theory using Dyson-Schwinger equations on a 4-dimensional torus. In particular, we demonstrate explicitly how the solutions for the gluon and the ghost propagator tend towards their respective infinite volume forms in the corresponding limit. This solves an important open problem of previous studies where the infinite volume limit led to an apparent mismatch, especially of the infrared behaviour, between torus extrapolations and the existing infinite volume solutions obtained in 4-dimensional Euclidean space-time. However, the correct infinite volume limit is approached rather slowly. The typical scales necessary to see the onset of the leading infrared behaviour emerging already imply volumes of at least 10-15 fm in lengths. To reliably extract the infrared exponents of the infinite volume solutions requires even much larger ones. While the volumes in the Monte-Carlo simulations available at present are far too small to facilitate that, we obtain a good qualitative agreement of our torus solutions with recent lattice data in comparable volumes.