Reactant adsorption in cyclic staircase voltammetry on spherical microelectrodes. Reversible redox reactions

On spherical microelectrodes, cyclic staircase voltammograms of reversible redox reactions complicated by the reactant adsorption depend on lateral interactions in the monolayer. Attraction forces increase the separation between the main wave and the post-peak, while the repulsion prevents the resolution of responses of the surface and volume reactions. The theoretical relationships between the dimensionless responses and the dimensionless adsorption constant, the relative surface adsorption capacity, the Frumkin coefficient and the electrode sphericity are given.     

Theory of a reversible redox reaction in an ionic liquid that is coupled to an ion transfer across the aqueous electrolyte/ionic liquid interface

A theory is provided for a reversible electro-oxidation of a neutral redox probe dissolved in room-temperature ionic liquid, which is sandwiched between an electrode surface and an aqueous solution as a thin film. If the peak potentials in cyclic voltammetry depend on the bulk concentration of electrolyte in water, the oxidation is most probably coupled to the transfer of anions from water into ionic liquid; but if the peak potentials are independent of the electrolyte concentration, the transfers of anions from water into ionic liquid and cations from ionic liquid into water are equally probable. Dedicated to Professor Dr. Yakov I. Tur’yan on the occasion of his 85th birthday.     

Simulation of differential pulse polarography of irreversible EC mechanism

A reversible electrode reaction that is followed by totally irreversible chemical reaction is investigated theoretically. The influence of chemical reaction on two components of the net response of differential pulse polarogram is analyzed. It is demonstrated that this EC mechanism depends on two kinetic parameters and that their critical values can be used for the measurement of the rate constant of chemical reaction.     

Higher-order breathers as quasi-rogue waves on a periodic background

Nonlinear Dynamics - We investigate higher-order breathers of the cubic nonlinear Schrödinger equation on a periodic elliptic background. We find that, beyond first order, any arbitrarily...     

Accelerating Airy–Gauss–Kummer localized wave packets

A general approach to generating three-dimensional nondiffracting spatiotemporal solutions of the linear Schrödinger equation with an Airy-beam time-dependence is reported. A class of accelerating optical pulses with the structure of Airy–Gauss–Kummer vortex beams is obtained. Our results demonstrate that the optical field contributions to the Airy–Gauss–Kummer accelerating optical wave packets of the cylindrical symmetry can be characterized by the radial and angular mode numbers.     

Solid state electrochemical reactions in systems with miscibility gaps

Cyclic voltammograms of electroactive solid compounds with partial immiscibility between the oxidized and reduced phases can exhibit a splitting of the peaks. If the free energy of transformation between the oxidized and reduced phases is small, the formal potentials of the redox pair will be almost the same in both solid phases. This results in an inert potential range in which no appreciable electrochemical activity is possible. The kinetic implications of this situation have been analysed in relation to the width of the miscibility gap. The diffusion of ions in the particle, which is hindered by the immiscibility, can proceed when a transition zone between the two phases exists in which the crystal structure is changed. If there is no such transition zone the voltammogram will display several spikes, which are caused by the collapse of concentration barriers at the sharp interfaces between the two phases in the mixed crystals. Received: 14 October 1999 / Accepted: 4 November 1999     

Modulation of the photonic band structure topology of a honeycomb lattice in an atomic vapor

In an atomic vapor, a honeycomb lattice can be constructed by utilizing the three-beam interference method. In the method, the interference of the three beams splits the dressed energy level periodically, forming a periodic refractive index modulation with the honeycomb profile. The energy band topology of the honeycomb lattice can be modulated by frequency detunings, thereby affecting the appearance (and disappearance) of Dirac points and cones in the momentum space. This effect can be usefully exploited for the generation and manipulation of topological insulators.