Water-Assisted Concerted Proton-Electron Transfer at Co(II)-Aquo Sites in Polyoxotungstates With Photogenerated RuIII(bpy)33+ Oxidant

The cobalt substituted polyoxotungstate [Co₆(H₂O)₂(α-B-PW₉O₃₄)₂(PW₆O₂₆)]¹⁷⁻ ( Co6 ) displays fast electron transfer (ET) kinetics to photogenerated Ru^III(bpy)₃³⁺, 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II) −OH ₂ and Co6(II) −OH, respectively, whose speciation in aqueous solution is associated to a pK_a of 7.6), and generates a Co(III)−OH moiety ( Co6(III) −OH), as proven by transient absorption spectroscopy; (ii) at pH>pK_a, the Co6(II) −OH→Ru^III(bpy)₃³⁺ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH <pK_a, the process involves Co6(II) − OH₂ → Co6(III)−OH transformation and proceeds via a multiple-site, concerted proton electron transfer (CPET) where water assists the transfer of the proton, as proven by the absence of effect of buffer base concentrations on the rate of the ET and by a H/D kinetic isotope in a range of 1.2–1.4. The reactivity of water is ascribed to its organization on the surface of the polyanionic scaffold through hydrogen bond networking involving the Co(II)−OH₂ group.     

Experimental and theoretical study of charge transfer in hydrogen ion scattering from a graphite surface

Ion scattering spectrometry (ISS) with time of flight (TOF) analysis is employed to measure the ion fraction of positively charged hydrogen (H⁺) projectiles scattered from a well characterized highly oriented pyrolitc graphite (HOPG) surface at a 45° scattering angle, various ingoing/outgoing angles and two different incoming energies (4 and 5 keV). In the theoretical approach, the negative ionization probability is calculated by employing a Green's function formalism to solve the dynamic collisional process. Both theoretical and experimental results are analyzed and contrasted. The theoretical negative ion fraction evolution during the collisional process is described in detail.     

Electron capture and loss in the scattering of H+ from HOPG graphite

In this paper we report measurements of the positive (H⁺) and negative (H^?) ion fractions after H⁺ scattering from a highly oriented pyrolytic graphite (HOPG) surface. The experimental results show that for a fixed (large) exit angle the negative fraction is almost independent of the primary ion energy, while the positive fraction increases steadily. For a fixed incident energy, the H⁺ and H^? fractions show a complementary behavior with exit angle. A dynamical quantum mechanical calculation, based on the localized and extended features of the atom–surface interaction, allows us to understand many of the features of the experimental results.     

Reversibility, Coarse Graining and the Chaoticity Principle

We describe a way of interpreting the chaotic principle of [GC1] more extensively than it was meant in the original works. Mathematically the analysis is based on the dynamical notions of Axiom A and Axiom B and on the notion of Axiom C, that we introduce arguing that it is suggested by the results of an experiment ([BGG]) on chaotic motions. Physically we interpret a breakdown of the Anosov property of a time reversible attractor (replaced, as a control parameter changes, by an Axiom A property) as a spontaneous breakdown of the time reversal symmetry: the relation between time reversal and the symmetry that remains after the breakdown is analogous to the breakdown of T-invariance while TCP still holds. Received: 28 February 1996 / Accepted: 12 February 1997     

Trapping an intensely bright, stable sonoluminescing bubble

Previous works on single bubble sonoluminescence in sulfuric acid solutions have stressed the fact that the sonoluminescence (SL) emissions are the highest ever found, but at the same time the bubble moves in orbits. We have fixed the SL bubble spatially and at the same time we have reached higher SL emissions using another harmonic acoustic signal to produce the acoustic excitation. Multiple harmonic excitation produces up to a fourfold increase in SL emissions, reaching the peak value of about 40 microW for a moving bubble and 15 microW for a nonmoving bubble. The ability to have a bright stationary bubble also opens new research opportunities. In particular, we develop a new method to measure the absolute radius evolution of the bubble that exploits this stability.     

Note on the Kaplan–Yorke Dimension and Linear Transport Coefficients

A number of new relations between the Kaplan–Yorke dimension, phase space contraction, transport coefficients and the maximal Lyapunov exponents are given for dissipative thermostatted systems, subject to a small but non-zero external field in a nonequilibrium stationary state. A condition for the extensivity of phase space dimension reduction is given. A new expression for the linear transport coefficients in terms of the Kaplan–Yorke dimension is derived. Alternatively, the Kaplan–Yorke dimension for a dissipative macroscopic system can be expressed in terms of the linear transport coefficients of the system. The agreement with computer simulations for an atomic fluid at small shear rates is very good.     

The interaction of background ocean air bubbles with a surface ship

A two-fluid model suitable for the calculation of the two-phase flow field around a naval surface ship is presented. This model couples the Reynolds-averaged Navier–Stokes (RANS) equations with equations for the evolution of the gas-phase momentum, volume fraction and bubble number density, thereby allowing the multidimensional calculation of the two-phase flow for monodisperse variable size bubbles. The bubble field modifies the liquid solution through changes in the liquid mass and momentum conservation equations. The model is applied to the case of the scavenging of wind-induced sea-background bubbles by an unpropelled US Navy frigate under non-zero Froude number boundary conditions at the free surface. This is an important test case, because it can be simulated experimentally with a model-scale ship in a towing tank. A significant modification of the background bubble field is predicted in the wake of the ship, where bubble depletion occurs along with a reduction in the bubble size due to dissolution. This effect is due to lateral phase distribution phenomena and the generation of an upwelling plume in the near wake that brings smaller bubbles up to the surface. © 1998 John Wiley & Sons, Ltd.     

Fast-field-cycling NMR study of magnetomechanically induced relaxation enhancement in ferrogelatine

We describe a field-cycling magnetic resonance experiment aimed to study the nuclear spinlattice relaxation in the simultaneous presence of an oscillating magnetic field and a magnetomechanically induced perturbation across the sample volume. The studied system is a gelatine doped with surfacted nanosize ferromagnetic particles. The spin system relaxes in coexistence with the magnetic interaction between the dopants and a weak external alternating magnetic field. Due to the interaction between the alternating field and the high magnetic moment of the dopants, a mechanical shaking of the particles becomes effective at low evolution fields. In this way, the particles act as local sonic sources, thus transmitting the vibrations to the gelic matrix where they are trapped. The impact produced on the molecular dynamics is observed through a magnetic resonance relaxation experiment. Saturation of the proton magnetization produced by the alternating magnetic field is also discussed. Results are compared with the direct effects produced by a pure sonic perturbation at the same frequency, introduced by coupling a piezoelectric transducer in direct contact with the sample.