Tuning of tetrahedrality in a silicon potential yields a series of monatomic (metal-like) glass formers of very high fragility

We obtain monatomic glass formers in simulations by modifying the tetrahedral character in a silicon potential to explore a triple point zone between potentials favoring diamond (dc) and bcc crystals. dc crystallization is always preceded by a polyamorphic transformation of the liquid, and is frustrated when the Kauzmann temperature of the high temperature liquid intersects the liquid-liquid coexistence line. The glass forming liquids are extraordinarily fragile. Our results suggest that Si and Ge liquids may be vitrified at a pressure close to the diamond-beta-tin-liquid triple point.     

Apparent First‐Order Liquid–Liquid Transition with Pre‐transition Density Anomaly,in Water‐Rich Ideal Solutions

The striking increases in response functions observed during supercooling of pure water have been the source of much interest and controversy. Imminent divergences of compressibility etc. unfortunately cannot be confirmed due to pre‐emption by ice crystallization. Crystallization can be repressed by addition of second components, but these usually destroy the anomalies of interest. Here we study systems in which protic ionic liquid second components dissolve ideally in water, and ice formation is avoided without destroying the anomalies. We observe a major heat capacity spike during cooling, which is reversed during heating, and is apparently of first order. It occurs just before the glassy state is reached and is preceded by water‐like density anomalies. We propose that it is the much‐discussed liquid–liquid transition previously hidden by crystallization. Fast cooling should allow the important fluctuations/structures to be preserved in the glassy state for leisurely investigation.     

On the Use of a Protic Ionic Liquid with a Novel Cation To Study Anion Basicity

The need for reliable means of ordering and quantifying the Lewis basicity of anions is discussed and the currently available methods are reviewed. Concluding that there is need for a simple impurity‐insensitive tool, we have sought, and here describe, a new method using NMR spectroscopy of a weak base, a substituted urea, 1,3‐dimethyl‐2‐imidazolidinone (DMI), as it is protonated by Brønsted acids of different strengths and characters. In all cases studied the product of protonation is a liquid (hence a protic ionic liquid). NMR spectroscopy detects changes in the electronic structure of the base upon interaction with the proton donors. As the proton‐donating ability, that is, acidity, increases, there is a smooth but distinct transition from a hydrogen‐bonded system (with no net proton transfer) to full ionicity. The liquid state of the samples and high concentration of nitrogen atoms, despite the very low natural abundance of its preferred NMR‐active isotope (¹⁵N), make possible the acquisition of ¹⁵N spectra in a relatively short time. These ¹⁵N, along with ¹³C, chemical shifts of the carbonyl atom, and their relative responses to protonation of the carbonyl oxygen, can be used as a means, sensitive to anion basicity and relatively insensitive to impurities, to sort anions in order of increasing hydrogen bond basicity. The order is found to be as follows: SbF₆^?<BF₄^?<NTf₂^?>ClO₄^?>FSO₃^?<TfO^?<HSO₄^?<Cl^?<MsO^?.     

Zum qualitativen Nachweis der Salpeters?ure

Ohne Zusammenfassung     

Ionic liquids as oxidic media for electron transfer studies

We review the basic ideas underlying the electron free energy level diagrams that have been found useful in considering the thermodynamics of redox processes in molten silicates and related high temperature ionic liquid (IL) solvents, and then show how closely they link to behavior observable in ambient temperature ionic liquids. Much of the information available on redox levels in molten oxides has been gleaned from chemical analysis and spectroscopic species distribution studies, but it is simpler to obtain the data electrochemically. Here, we report some cyclic voltammetry measurements of the Fe(II)∕Fe(III) redox equilibrium in aprotic ionic liquids whose anions provide oxide environments for the redox species that are of different electronic polarizability character from the high temperature solvents, and relate the observations to those of the earlier studies. Quasi-reversible behavior is found in each of the cases studied. As might be expected, the Fe(II)∕Fe(III) equilibrium experiences a more basic environment in an acetate IL than it experiences in any of the common glassforming oxide media, while triflate anions contrast by providing a more acid environment than does the most acid of the molten oxide glassformers studied (an alkali phosphate). The difference can amount to well over 1 V, suggesting the possibility of a "basicity cell" where the same redox couple locates in anode and cathode compartments of the cell, and only the anion environment is different.     

Einen Universalreagensglashalter

Ohne Zusammenfassung     

Lewis Acid-Promoted Oxidative Addition at a [Ni0(diphosphine)2] Complex: The Critical Role of a Secondary Coordination Sphere

Oxidative addition represents a critical elementary step in myriad catalytic transformations. Here, the importance of thoughtful ligand design cannot be overstated. In this work, we report the intermolecular activation of iodobenzene (PhI) at a coordinatively saturated 18-electron [Ni⁰(diphosphine)₂] complex bearing a Lewis acidic secondary coordination sphere. Whereas alkyl-substituted diphosphine complexes of Group 10 are known to be unreactive in such reactions, we show that [Ni⁰(P₂B^Cy₄)₂] (P₂B^Cy₄=1,2-bis(di(3-dicyclohexylboraneyl)-propylphosphino)ethane) is competent for room-temperature PhI cleavage to give [Ni^II(P₂B^Cy₄)(Ph)(I)]. This difference in oxidative addition reactivity has been scrutinized computationally – an outcome that is borne out in ring-opening to provide the reactive precursor – for [Ni⁰(P₂B^Cy₄)₂], a “boron-trapped” 16-electron κ¹-diphosphine Ni(0) complex. Moreover, formation of [Ni^II(P₂B^Cy₄)(Ph)(I)] is inherent to the P₂B^Cy₄ secondary coordination sphere: treatment of the Lewis adduct, [Ni⁰(P₂B^Cy₄)₂(DMAP)₈] with PhI provides [Ni^II(P₂B^Cy₄)₂(DMAP)₈(I)]I via iodine-atom abstraction and not a [Ni^II(Ph)(I)(diphosphine)] compound – an unusual secondary sphere effect. Finally, the reactivity of [Ni⁰(P₂B^Cy₄)₂] with 4-iodopyridine was surveyed, which resulted in a pyridyl-borane linked oligomer. The implications of these outcomes are discussed in the context of designing strongly donating, and yet labile diphosphine ligands for use in a critical bond activation step relevant to catalysis.     

Quantum quenches in a spinor condensate

We discuss the ordering of a spin-1 condensate when quenched from its paramagnetic phase to its ferromagnetic phase by reducing the magnetic field. We first elucidate the nature of the equilibrium quantum phase transition. Quenching rapidly through this transition reveals XY ordering either at a specific wave vector, or the "light-cone" correlations familiar from relativistic theories, depending on the end point of the quench. For a quench proceeding at a finite rate the ordering scale is governed by the Kibble-Zurek mechanism. The creation of vortices through growth of the magnetization fluctuations is also discussed. The long-time dynamics again depends on the end point, conserving the order parameter in a zero field, but not at a finite field, with differing exponents for the coarsening of magnetic order. The results are discussed in the light of a recent experiment by Sadler et al.