Beyond the Butler-Volmer equation. Curved Tafel slopes from steady-state current-voltage curves

We report the discovery and analysis of curved Tafel slopes from the electrochemical reduction of hexamminecobalt(III) under steady-state conditions. In order to confirm the existence of the curvature, random assemblies of carbon microelectrodes (RAM? electrodes) were employed to obtain experimental data over more than three orders of magnitude, without significant double layer charging currents and without ohmic distortion. Since the rate-determining step in the reduction reaction is electron transfer, and no ligand substitution reactions occur on the timescale of experiments, the curvature of the Tafel plot is attributed to the dependence of the symmetry factor on electrode potential.     

A novel lyotropic liquid crystal formed by triphilic star-polyphiles: hydrophilic/oleophilic/fluorophilic rods arranged in a 12.6.4. tiling

Triphilic star-polyphiles are short-chain oligomeric molecules with a radial arrangement of hydrophilic, hydrocarbon and fluorocarbon chains linked to a common centre. They form a number of liquid crystalline structures when mixed with water. In this contribution we focus on a hexagonal liquid crystalline mesophase found in star-polyphiles as compared to the corresponding double-chain surfactant to determine whether the hydrocarbon and fluorocarbon chains are in fact demixed in these star-polyphile systems, or whether both hydrocarbon and fluorocarbon chains are miscible, leading to a single hydrophobic domain, making the star-polyphile effectively amphiphilic. We report SANS contrast variation data that are compatible only with the presence of three distinct immiscible domains within this hexagonal mesophase, confirming that these star-polyphile liquid crystals are indeed hydrophilic/oleophilic/fluorophilic 3-phase systems. Quantitative comparison with scattering simulations shows that the experimental data are in very good agreement with an underlying 2D columnar (12.6.4) tiling. As in a conventional amphiphilic hexagonal mesophase, the hexagonally packed water channels (dodecagonal prismatic domains) are embedded in a hydrophobic matrix, but that matrix is split into oleophilic hexagonal prismatic domains and fluorophilic quadrangular prismatic domains.     

Detection of pentatetraene by reaction of the ethynyl radical (C2H) with allene (CH2=C=CH2) at room temperature

The reaction of ethynyl radical (C(2)H) with allene (C(3)H(4)) at room temperature is investigated using an improved synchrotron multiplexed photoionization mass spectrometer (MPIMS) coupled to tunable vacuum ultraviolet (VUV) synchrotron radiation from the Advanced Light Source at the Lawrence Berkeley National Laboratory (LBNL). The orthogonal-accelerated time-of-flight mass spectrometer (OA-TOF) compared to the magnetic sector mass spectrometer used in a previous investigation of the title reaction (Phys. Chem. Chem. Phys., 2007, 9, 4291) enables more sensitive and selective detection of low-yield isomeric products. The C(5)H(4) isomer with the lowest ionization energy, pentatetraene, is now identified as a product of the reaction. Pentatetraene is predicted to be formed based on recent ab initio/RRKM calculations (Phys. Chem. Chem. Phys., 2010, 12, 2606) on the C(5)H(5) potential energy surface. However, the computed branching fraction for pentatetraene is predicted to be five times higher than that for methyldiacetylene, whereas experimentally the branching fraction of pentatetraene is observed to be small compared to that of methyldiacetylene. Although H-atom assisted isomerization of the products can affect isomer distribution measurements, isomerization has a negligible effect in this case. The kinetic behavior of the several C(5)H(4) isomers is identical, as obtained by time-dependent photoionization spectra. Even for high allene concentrations (and hence higher H-atom concentrations) no decay of the pentatetraene fraction is observed, indicating that H-assisted isomerization of pentatetraene to methyldiacetylene does not account for the difference between the experimental data and the theoretical branching ratios.     

Electronic state selectivity in dication-molecule single electron transfer reactions: NO(2+) + NO

The single-electron transfer reaction between NO(2+) and NO, which initially forms a pair of NO(+) ions, has been studied using a position-sensitive coincidence technique. The reactivity in this class of collision system, which involves the interaction of a dication with its neutral precursor, provides a sensitive test of recent ideas concerning electronic state selectivity in dicationic single-electron transfer reactions. In stark contrast to the recently observed single-electron transfer reactivity in the analogous CO(2)(2+)/CO(2) and O(2)(2+)/O(2) collision systems, electron transfer between NO(2+) and NO generates two product NO(+) ions which behave in an identical manner, whether the ions are formed from NO(2+) or NO. This observed behaviour is in excellent accord with the recently proposed rationalization of the state selectivity in dication-molecule SET reactions using simple propensity rules involving one-electron transitions.     

Deceleration of supersonic beams using inhomogeneous electric and magnetic fields

Methods for the production of cold atomic and molecular samples relying on the deceleration of pulsed supersonic beams are described and a review of the corresponding literature is presented. These methods include multistage Stark deceleration, multistage Zeeman deceleration, and Rydberg-Stark deceleration. Recent applications of the cold samples produced with these techniques are summarized.     

Bis(5,7‐dimethyl‐8‐hydroxyquinolinato)platinum(II) Complex for Efficient Organic Heterojunction Solar Cells

Organic photovoltaic (OPV) cells using metal(II) (Pt, Pd, Cu, and Ni) chelates of 8‐hydroxyquinoline (Hq) or 5,7‐dimethyl‐8‐hydroxy‐quinoline (HMe₂q) as an electron donor were fabricated by vacuum deposition. The bis(5,7‐dimethyl‐8‐hydroxyquinolinato)platinum(II) [Pt(Me₂q)₂]‐based OPVs showed the best performance with an open voltage (V_OC) of 0.42 V, a short circuit current density (J_SC) of 14.8 mA cm^?2, and a maximum power conversion efficiency (η_P) of 2.4 %. The X‐ray single‐crystal structures together with the grazing incidence X‐ray diffraction (GIXRD) data of thin film samples reveal that the peripheral methyl substituent(s) and platinum(II) ion are essential for the high degree of film crystallinity resulting in improved performance of the as‐fabricated field‐effect transistors (FETs) and OPV cells.     

Organo‐ and Hydrogelators Based on Luminescent Monocationic Terpyridyl Platinum(II) Complexes with Biphenylacetylide Ligands

A series of phosphorescent terpyridyl platinum(II) complexes with ancillary biphenylacetylide ligands, namely, [(R₃tpy)PtC≡C(biphenyl)]X (R=tBu, H, or Et₂N; tpy=2,2′;6′,2′′‐terpyridyl; X is an anion) were synthesized and structurally characterized by various spectroscopic techniques and X‐ray diffraction methods. Despite a lack of long alkyl chain(s) or hydrogen‐bonding motif(s), complexes [(tpy)PtC≡C(biphenyl)]Cl and [(tBu₃tpy)PtC≡C(biphenyl)]X (X=Cl, ClO₄, PF₆, or BF₄) were found to gelate water and organic solvents, respectively. The self‐aggregation of these complexes in solutions and the resulting gels were investigated with variable‐temperature (VT) ¹H NMR spectroscopy, polarized optical microscopy, and absorption/emission spectroscopy. SEM micrographs on dry gels revealed entangled nanofibers with diameters of 20–40 nm and lengths of tens of micrometers. Powder X‐ray diffraction (PXRD) study revealed various degrees of crystallinity of these fibrillar nanostructures. The substituents on both the terpyridyl and acetylide ligands and counterion of these complexes play a profound but concerted role in tuning the intermolecular metal???metal and/or π–π interactions, and hence the gelation properties.     

On stress-state dependent plasticity modeling: Significance of the hydrostatic stress, the third invariant of stress deviator and the non-associated flow rule

It has been shown that the plastic response of many materials, including some metallic alloys, depends on the stress state. In this paper, we describe a plasticity model for isotropic materials, which is a function of the hydrostatic stress as well as the second and third invariants of the stress deviator, and present its finite element implementation, including integration of the constitutive equations using the backward Euler method and formulation of the consistent tangent moduli. Special attention is paid for the adoption of the non-associated flow rule. As an application, this model is calibrated and verified for a 5083 aluminum alloy. Furthermore, the Gurson-Tvergaard-Needleman porous plasticity model, which is widely used to simulate the void growth process of ductile fracture, is extended to include the effects of hydrostatic stress and the third invariant of stress deviator on the matrix material.     

Twistor Geometry of a Pair of Second Order ODEs

We discuss the twistor correspondence between path geometries in three dimensions with vanishing Wilczynski invariants and anti-self-dual conformal structures of signature (2, 2). We show how to reconstruct a system of ODEs with vanishing invariants for a given conformal structure, highlighting the Ricci-flat case in particular. Using this framework, we give a new derivation of the Wilczynski invariants for a system of ODEs whose solution space is endowed with a conformal structure. We explain how to reconstruct the conformal structure directly from the integral curves, and present new examples of systems of ODEs with point symmetry algebra of dimension four and greater which give rise to anti–self–dual structures with conformal symmetry algebra of the same dimension. Some of these examples are (2, 2) analogues of plane wave space–times in General Relativity. Finally we discuss a variational principle for twistor curves arising from the Finsler structures with scalar flag curvature.