Probing Ag nanoparticle surface oxidation in contact with (in)organics: an X‐ray scattering and fluorescence yield approach

Characterizing interfacial reactions is a crucial part of understanding the behavior of nanoparticles in nature and for unlocking their functional potential. Here, an advanced nanostructure characterization approach to study the corrosion processes of silver nanoparticles (Ag‐Nps), currently the most highly produced nanoparticle for nanotechnology, is presented. Corrosion of Ag‐Nps under aqueous conditions, in particular in the presence of organic matter and halide species common to many natural environments, is of particular importance because the release of toxic Ag⁺ from oxidation/dissolution of Ag‐Nps may strongly impact ecosystems. In this context, Ag‐Nps capped with polyvinolpyrrolidone (PVP) in contact with a simple proxy of organic matter in natural waters [polyacrylic acid (PAA) and Cl^? in solution] has been investigated. A combination of synchrotron‐based X‐ray standing‐wave fluorescence yield‐ and X‐ray diffraction‐based experiments on a sample consisting of an approximately single‐particle layer of Ag‐Nps deposited on a silicon substrate and coated by a thin film of PAA containing Cl revealed the formation of a stable AgCl corrosion product despite the presence of potential surface stabilizers (PVP and PAA). Diffusion and precipitation processes at the Ag‐Nps–PAA interface were characterized with a high spatial resolution using this new approach.     

Optical scar in a chaotic fiber

We propose to use a multimode optical fiber with a D-shaped cross section as a privileged system to image wavefunctions of a chaotic system. Scar modes are in particular the subject of our investigations. We study their imprints on the statistics of intensity and we show how the introduction of a localized gain region in the fiber is used to perform a selective amplification of scar modes.     

Production and signature of intermediate vector bosons

The front-back asymmetry of outgoing muons in the inclusive reaction $\text{p}\text{p}\text{→ Z(→ μ}{}^{\mathrm{+}}\text{μ}{}^{\mathrm{?}}\text{)+}$ anything is calculated in the framework of the Drell-Yan model. We get very general expressions for the front-back asymmetry and the differential cross section in terms of the weak coupling constants and the parton distributions. Results for W^± production and proton-proton collisions are also given. Numerical estimates are made using various parton distributions and the Weinberg-Salam model for definiteness. We comment on the predictions of gauge theories that accommodate the absence of parity violating effects in atomic physics. We also give a new estimate of the inclusive cross sections $\text{p}\text{p}$ or pp → Z(→ μ⁺μ^?) or W^±(→ μ^±ν_μ) + anything. The effects of asymptotic freedom in the frontback asymmetries and the total cross sectons are investigated. We reanalyze results for the purely leptonic reaction e⁺e^? → γ, Z → μ⁺μ^?.     

Entropy-driven formation of the gyroid cubic phase

We show, by computer simulation, that tapered or pear-shaped particles, interacting through purely repulsive interactions, can freely self-assemble to form the three-dimensionally periodic, gyroid cubic phase. The Ia3d gyroid cubic phase is formed by these particles on both compression of an isotropic configuration and expansion of a smectic A bilayer arrangement. For the latter case, it is possible to identify the steps by which the topological transformation from nonintersecting planes to fully interpenetrating, periodic networks takes place.     

Topological and Steric Constraints to Stabilize Heteroleptic Copper(I) Complexes Combining Phenanthroline Ligands and Phosphines

Heteroleptic copper(I) complexes combining phenanthroline derivatives (NN) and chelating bisphosphine ligands (PP) are an important class of luminescent materials for various applications. Although thermodynamically stable, [Cu(NN)(PP)]⁺ derivatives are also kinetically unstable. As a result, a dynamic ligand-exchange reaction is often observed in solution, leading to a dynamic mixture of heteroleptic and homoleptic complexes. To prevent the formation of the homoleptic species, macrocyclic phenanthroline ligands have been used for the preparation of [Cu(NN)(PP)]⁺ pseudorotaxanes. The topological constraint resulting from the macrocyclic structure of the NN ligand drives the thermodynamic equilibrium towards the exclusive formation of the heteroleptic complex as long as the macrocycle is large and flexible enough to allow for the threading of the PP ligand. Conversely, when the threading is prevented by steric constraints, unprecedented copper(I) complexes with a trigonal coordination geometry are obtained. These results are summarized in the present concept article.     

In memoriam: Boris Dubrovin

Letters in Mathematical Physics -     

Hydrodynamic modes in a gas of magnons

Density waves analogous to second sound are studied in a gas of magnons. Quasiparticle interaction is considered for both equilibrium and non equilibrium thermodynamics. The non equilibrium theory is based on a Boltzmann equation for magnon-magnon scattering. Contrary to the total energy and magnetization, (quasi)-momentum is not strictly conserved. In the hydrodynamic regime, the transport equation is reduced to a set of two coupled equations for the magnetization and the local temperature. For low temperatures these have diffusive and propagating solutions while for high temperatures, where momentum is dissipated by Umklapp processes, the solutions are only diffusive. The magnetization response function and the corresponding spectral function are discussed for various wavenumbers and temperatures.     

Simulation of certain multivariate generalized Pareto distributions

The investigation of multivariate generalized Pareto distributions (GPDs) has begun only recently. For further progress with these distributions simulation methods are an important part. We describe several methods of simulating GPDs, beginning with an efficient method for the logistic GPD. The algorithm is based on the Shi transformation, which was already used for the simulation of multivariate extreme value distributions (EVDs) of logistic type. In the sequel another algorithm is presented simulating a broader class of GPDs. Due to its numerical complexity it is only practicably applicable in low dimensions. A method is given to generate unconditional GPD random vectors from conditionally GPD distributed random vectors. A short application of the simulation methods in the analysis of a real hydrological data set concludes the article. The simulation algorithms are available on the author’s home page .      

Path Relinking, Cycle-Based Neighbourhoods and Capacitated Multicommodity Network Design

In this paper, we propose a path relinking procedure for the fixed-charge capacitated multicommodity network design problem. Cycle-based neighbourhoods are used both to move along paths between elite solutions and to generate the elite candidate set by a tabu-like local search procedure. Several variants of the method are implemented and compared. Extensive computational experiments indicate that the path relinking procedure offers excellent results. It systematically outperforms the cycle-based tabu search method in both solution quality and computational effort and offers the best current meta-heuristic for this difficult class of problems.