Kinetics of Central Ion Electroreduction in Cerium (IV)-Decatungstate

A general characteristics is given to the kinetics of electroreduction of cerium-decatugstate anions on mercury, polycrystalline gold, and the pyrolytic-graphite basis plane in acetate buffer solutions (pH 3.5-6.0). Based on the analysis of UV absorption spectra, the ratio of two reactant forms differing in the protonation degree in solutions under study is estimated. At a negatively charged mercury electrode, the reduction of the Ce(IV) central ion is shown to proceed as an outer-sphere process with classical manifestations of the psi-prime effect (polarization curves reveal a current minimum which deepens with supporting electrolyte dilution and an increase in the reactant negative charge). On the positively charged surface, the current is observed to increase with an increase in the supporting electrolyte concentration, which is interpreted in terms of the strong adsorption of the reactant and its coadsorption with cations. The gold electrode demonstrates pronounced effects of strong chemisorption. Adsorption complications observed on pyrolytic graphite are shown to become strongther for surfaces with more pronounced nonideal behavior. For low concentrations of atomar steps (apparently, for low coverages of pyrolytic-graphite surface with the adsorbed reactant), the quasireversible electron transfer with the rate increasing with increasing pH is observed.     

Modulation of Gravity Waves with Shear in Water

The effect of water shear on the stability of infinitesimal perturbations (in the form of side bands) to a finite-amplitude gravity wave is investigated both numerically and analytically. The shear is modeled by a piecewise-linear velocity profile. Nonlinear cubic Schrödinger equation for the wave envelope of a slowly varying wave train is derived. It is shown that depending on the direction of propagation (along or against the shear) of the finite-amplitude waves, the effect of shear on the stability is substantially different. In most cases, however, the shear strength increase first enhances, but later suppresses, the instability.     

Eckart axis conditions and the minimization of the root-mean-square deviation: two closely related problems

We highlight the fact that the rotation matrix minimizing the root-mean-square deviation between two molecular conformations [W. Kabsch, Acta Cryst. A32, 922 (1976)] also satisfies the Eckart axis conditions [C. Eckart, Phys. Rev. 47, 552 (1935)].     

The effect of the surface enhanced polariton field on the tunneling current of a STM

The influence of surface polaritons (SPs), excited on the external (fast mode) and internal (slow mode) surfaces of a gold film, on the tunneling current of a STM is investigated. The role of the surface polaritons is directly demonstrated by the angular excitation spectra of the induced tunneling current. Possible mechanisms which might give rise to the SP induced change in the tunneling current are discussed. An electromagnetic field of SPs within a tunneling gap is estimated to be surface enhanced in order to explain the value of the induced tunneling current. Images of the polariton induced signal distribution over the sample surface taken by means of different SP modes are compared in order to obtain information on the structure of the internal surface of the film.     

Molecular dynamics simulation of zirconia melting

The melting point for the tetragonal and cubic phases of zirconia (ZrO₂) was computed using Z-method microcanonical molecular dynamics simulations for two different interaction models: the empirical Lewis-Catlow potential versus the relatively new reactive force field (ReaxFF) model. While both models reproduce the stability of the cubic phase over the tetragonal phase at high temperatures, ReaxFF also gives approximately the correct melting point, around 2900 K, whereas the Lewis-Catlow estimate is above 6000 K.