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.     

The numerical integration of relative equilibrium solutions. The nonlinear Schrodinger equation

We analyse different error propagation mechanisms for conservativeand nonconservative time-integrators of nonlinear Schrödingerequations. We use a geometric approach based on interpretingwaves as relative equilibria.     

A search for stable particles heavier than the proton and for Q = −23 quarks produced in e+e− annihilation

We have searched 1.4 × 10⁶e⁺e^? annihilation events for particles with 1–3 GeV/c² mass and charge $\text{Q = ?}\text{2}\text{3}$ from the processes e⁺e^?→q$\text{q}$X and e⁺e^? → q$\text{q}$. Upper limits of RQ ～ 10^?4 for each process are presented which improve the previous limits on free quark production in electromagnetic interactions by 2 orders of magnitude.     

Observation of the radiative transition ψ → γE(1420)

We have observed a radiative transition from the ψ to a state decaying into K_SK^±π^?, with mass M = 1.44_?0.015^+0.01 GeV/c² and width Γ = 0.05_?0.02^+0.03 GeV/c². We tentatively identify this state as the E(1420). Assuming that this state is an isospin singlet, we have determined the branching fraction product $\text{B(ψ → γ}\text{E}\text{) × B(}\text{E}\text{×}\text{K}\text{K}\text{π) = (3.6 ± 1.4) × 10}{}^{\mathrm{?3}}$.