Elemental chemical analysis of submerged targets by double-pulse laser-induced breakdown spectroscopy

Double-pulse laser-induced plasma spectroscopy (DP-LIPS) is applied to submerged targets to investigate its feasibility for elemental analysis. The role of experimental parameters, such as inter-pulse delay and detection time, has been discussed in terms of the dynamics of the laser-induced bubble produced by the first pulse and its confinement effect on the plasma produced by the second laser pulse. The analytical performance of this technique applied to targets in a water environment are discussed. The elemental analysis of submerged copper alloys by DP-LIPS has been compared with conventional (single-pulse) LIBS in air. Theoretical investigation of the plasma dynamics in water bubbles and open air has been performed.     

RBFOpt: an open-source library for black-box optimization with costly function evaluations

We consider the problem of optimizing an unknown function given as an oracle over a mixed-integer box-constrained set. We assume that the oracle is expensive to evaluate, so that estimating partial derivatives by finite differences is impractical. In the literature, this is typically called a black-box optimization problem with costly evaluation. This paper describes the solution methodology implemented in the open-source library RBFOpt, available on COIN-OR. The algorithm is based on the Radial Basis Function method originally proposed by Gutmann (J Glob Optim 19:201–227, 2001.  https://doi.org/10.1023/A:1011255519438), which builds and iteratively refines a surrogate model of the unknown objective function. The two main methodological contributions of this paper are an approach to exploit a noisy but less expensive oracle to accelerate convergence to the optimum of the exact oracle, and the introduction of an automatic model selection phase during the optimization process. Numerical experiments show that RBFOpt is highly competitive on a test set of continuous and mixed-integer nonlinear unconstrained problems taken from the literature: it outperforms the open-source solvers included in our comparison by a large amount, and performs slightly better than a commercial solver. Our empirical evaluation provides insight on which parameterizations of the algorithm are the most effective in practice. The software reviewed as part of this submission was given the Digital Object Identifier (DOI)  https://doi.org/10.5281/zenodo.597767.     

Representation of MV-algebras by regular ultrapowers of [0, 1]

We present a uniform version of Di Nola Theorem, this enables to embed all MV-algebras of a bounded cardinality in an algebra of functions with values in a single non-standard ultrapower of the real interval [0,1]. This result also implies the existence, for any cardinal α, of a single MV-algebra in which all infinite MV-algebras of cardinality at most α embed. Recasting the above construction with iterated ultrapowers, we show how to construct such an algebra of values in a definable way, thus providing a sort of “canonical” set of values for the functional representation.     

An integral formulation procedure for the solutions to Helmholtz's equation in spherically symmetric media

Starting from Helmholtz's equation in inhomogeneous media, the associated radial second‐order equation is investigated through a Volterra integral equation. First the integral equation is considered in a sphere. Boundedness, uniqueness and existence of the (regular) solution are established and the series form of the solution is provided. An estimate is determined for the error arising when the series is truncated. Next the analogous problem is considered for a spherical layer. Again, boundedness, uniqueness and existence of two base solutions are established and error estimates are determined. The procedure proves more effective in the sphere. Copyright © 2009 John Wiley & Sons, Ltd.     

Extended formulations in combinatorial optimization

This survey is concerned with the size of perfect formulations for combinatorial optimization problems. By “perfect formulation”, we mean a system of linear inequalities that describes the convex hull of feasible solutions, viewed as vectors. Natural perfect formulations often have a number of inequalities that is exponential in the size of the data needed to describe the problem. Here we are particularly interested in situations where the addition of a polynomial number of extra variables allows a formulation with a polynomial number of inequalities. Such formulations are called “compact extended formulations”. We survey various tools for deriving and studying extended formulations, such as Fourier’s procedure for projection, Minkowski-Weyl’s theorem, Balas’ theorem for the union of polyhedra, Yannakakis’ theorem on the size of an extended formulation, dynamic programming, and variable discretization. For each tool that we introduce, we present one or several examples of how this tool is applied. In particular, we present compact extended formulations for several graph problems involving cuts, trees, cycles and matchings, and for the mixing set, and we present the proof of Fiorini, Massar, Pokutta, Tiwary and de Wolf of an exponential lower bound for the cut polytope. We also present Bienstock’s approximate compact extended formulation for the knapsack problem, Goemans’ result on the size of an extended formulation for the permutahedron, and the Faenza-Kaibel extended formulation for orbitopes.     

“Through-Space” Relativistic Effects on NMR Chemical Shifts of Pyridinium Halide Ionic Liquids

We have investigated, using two-component relativistic density functional theory (DFT) at ZORA-SO-BP86 and ZORA-SO-PBE0 level, the occurrence of relativistic effects on the ¹H, ¹³C, and ¹⁵N NMR chemical shifts of 1-methylpyridinium halides [MP][X] and 1-butyl-3-methylpyridinium trihalides [BMP][X₃] ionic liquids (ILs) (X=Cl, Br, I) as a result of a non-covalent interaction with the heavy anions. Our results indicate a sizeable deshielding effect in ion pairs when the anion is I⁻ and I₃⁻. A smaller, though nonzero, effect is observed also with bromine while chlorine based anions do not produce an appreciable relativistic shift. The chemical shift of the carbon atoms of the aromatic ring shows an inverse halogen dependence that has been rationalized based on the little C-2s orbital contribution to the σ-type interaction between the cation and anion. This is the first detailed account and systematic theoretical investigation of a relativistic heavy atom effect on the NMR chemical shifts of light atoms in the absence of covalent bonds. Our work paves the way and suggests the direction for an experimental investigation of such elusive signatures of ion pairing in ILs.     

Memory effects in quantum channel discrimination

We consider quantum-memory assisted protocols for discriminating quantum channels. We show that for optimal discrimination of memory channels, memory assisted protocols are needed. This leads to a new notion of distance for channels with memory, based on the general theory of quantum testers. For discrimination and estimation of sets of independent unitary channels, we prove optimality of parallel protocols among all possible architectures.     

Use of Nitrogen-Doped Carbon Nanodots for the Photocatalytic Fluoroalkylation of Organic Compounds

The use of amine-rich N-doped carbon nanodots (NCNDs) for the photochemical radical perfluoroalkylation of organic compounds is reported. This operationally simple approach occurs under mild conditions producing valuable new C−C bonds. The chemistry is driven by the ability of NCNDs to directly reach an electronically excited state upon light absorption, thereby successively triggering the formation of reactive radical species from simple perfluoroalkyl iodides. Preliminary mechanistic studies are also reported.     

Electrochemically deposited ZnO films: an XPS study on the evolution of their surface hydroxide and defect composition upon thermal annealing

Electrodeposition from ZnCl₂ aqueous solution was performed to grow ZnO thin films on the surface of polycrystalline copper plates. Electrochemical parameters for deposition were optimized by means of cyclic voltammetry (CV). The morphology of the deposits was studied via scanning electron microscopy (SEM), and their chemical composition was ascertained by means of X-ray photoelectron spectroscopy (XPS). The effects of changing the deposition bath temperature (T _bath) and the role played by post-deposition treatments, such as temperature and time of annealing in air, were studied. SEM images of freshly deposited vs. annealed samples have shown that in the former case the films display a rough morphology with mixed grain/hexagonal platelets structures and in the latter smaller but more uniformly dispersed cubic grains. T _bath is found to be the key parameter to induce the different morphology in the deposited films, which reflects in a different chemical reactivity of surface species, as found on the basis of the binding energies and relative quantitative ratios between Zn 2p and O 1s peaks. In fact, a higher T _bath favours a more efficient desorption of OH groups upon annealing, the O 1s peak resulting to much more drastically modified oxide/hydroxide intensity ratio with respect to the case of the sample deposited at lower T _bath.     

1,2‐Dimethoxyethane Degradation Thermodynamics in Li−O2 Redox Environments

The reaction thermodynamics of the 1,2‐dimethoxyethane (DME), a model solvent molecule commonly used in electrolytes for Li?O₂ rechargeable batteries, has been studied by first‐principles methods to predict its degradation processes in highly oxidizing environments. In particular, the reactivity of DME towards the superoxide anion O₂^? in oxygen‐poor or oxygen‐rich environments is studied by density functional calculations. Solvation effects are considered by employing a self‐consistent reaction field in a continuum solvation model. The degradation of DME occurs through competitive thermodynamically driven reaction paths that end with the formation of partially oxidized final products such as formaldehyde and methoxyethene in oxygen‐poor environments and methyl oxalate, methyl formate, 1‐formate methyl acetate, methoxy ethanoic methanoic anhydride, and ethylene glycol diformate in oxygen‐rich environments. This chemical reactivity indirectly behaves as an electroactive parasitic process and therefore wastes part of the charge exchanged in Li?O₂ cells upon discharge. This study is the first complete rationale to be reported about the degradation chemistry of DME due to direct interaction with O₂^?/O₂ molecules. These findings pave the way for a rational development of new solvent molecules for Li?O₂ electrolytes.