Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .2. Effect of the ionic size of supporting electrolytes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene in MPEG/salt electrolytes were determined by using steady-state voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equation. The effect of the ionic size of six supporting electrolytes on diffusion and electron transfer dynamics of ferrocene was discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .3. Effect of the polymer solvents

The diffusion coefficients(D-app) and the heterogeneous electron transfer rate constants(k(s)) for ferrocene in several polymer solvents were determined by using steady-state voltammetry. The temperature dependence of the two parameters indicates Arrhenius behavior, The polymer solvent effects on diffusion and electron transfer dynamics of ferrocene were discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .1. Effect of the nature of electroactive solutes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steady-state voltammetry. The two parameters increase with increasing temperature, indicating Arrhenius behavior. The effects of the nature of electroactive solute molecules on D-app, k(s), and the half-wave potentials(E-1/2) are discussed.

Measurements of temperature dynamics of ions trapped inside an electron beam ion trap and evidence for ionisation heating

A technique is described whereby measurements of ions extracted from an electron beam ion trap can be used to deduce their temperature dynamics. The measured temperature dynamics shows the expected trend as a function of charge and also gives evidence for Landau-Spitzer heating, ionization heating and evaporative cooling.

Correlated electron-ion dynamics with open boundaries: formalism

We extend a new formalism, which allows correlated electron-ion dynamics to be applied to the problem of open boundary conditions. We implement this at the first moment level (allowing heating of ions by electrons) and observe the expected cooling in the classical part of the ionic kinetic energy and current-induced heating in the quantum contribution. The formalism for open boundaries should be easily extended to higher moments of the correlated electron-ion fluctuations.

Correlated electron-ion dynamics: the excitation of atomic motion by energetic electrons

Correlated electron-ion dynamics (CEID) is an extension of molecular dynamics that allows us to introduce in a correct manner the exchange of energy between electrons and ions. The formalism is based on a systematic approximation: small amplitude moment expansion. This formalism is extended here to include the explicit quantum spread of the ions and a generalization of the Hartree-Fock approximation for incoherent sums of Slater determinants. We demonstrate that the resultant dynamical equations reproduce analytically the selection rules for inelastic electron-phonon scattering from perturbation theory, which control the mutually driven excitations of the two interacting subsystems. We then use CEID to make direct numerical simulations of inelastic current-voltage spectroscopy in atomic wires, and to exhibit the crossover from ionic cooling to heating as a function of the relative degree of excitation of the electronic and ionic subsystems.

Inelastic quantum transport in nanostructures: The self-consistent Born approximation and correlated electron-ion dynamics

A dynamical method for inelastic transport simulations in nanostructures is compared to a steady-state method based on nonequilibrium Green's functions. A simplified form of the dynamical method produces, in the steady state in the weak-coupling limit, effective self-energies analogous to those in the Born approximation due to electron-phonon coupling. The two methods are then compared numerically on a resonant system consisting of a linear trimer weakly embedded between metal electrodes. This system exhibits an enhanced heating at high biases and long phonon equilibration times. Despite the differences in their formulation, the static and dynamical methods capture local current-induced heating and inelastic corrections to the current with good agreement over a wide range of conditions, except in the limit of very high vibrational excitations where differences begin to emerge.

Correlated electron-ion dynamics in metallic systems

In this paper we briefly discuss the problem of simulating non-adiabatic processes in systems that are usefully modelled using molecular dynamics. In particular we address the problems associated with metals, and describe two methods that can be applied: the Ehrenfest approximation and correlated electron-ion dynamics (CEID). The Ehrenfest approximation is used to successfully describe the friction force experienced by an energetic particle passing through a crystal, but is unable to describe the heating of a wire by an electric current. CEID restores the proper heating.

Dynamics of nonlinearly coupled magnetic-field-aligned electromagnetic electron-cyclotron waves near the zero-group-dispersion point in magnetized plasmas

The nonlinear coupling between two magnetic-field-aligned electromagnetic electron-cyclotron (EMEC) waves in plasmas is considered. Evaluating the ponderomotive coupling between the EMEC waves and quasistationary plasma density perturbations, a pair of coupled nonlinear Schrodinger equations (CNLSEs) is obtained. The CNLSEs are then used to investigate the occurrence of modulational instability in magnetized plasmas. Waves in the vicinity of the zero-group-dispersion point are considered, so that the group dispersion terms may either bear the same or different signs. It is found that a stable EMEC wave can be destabilized due to its nonlinear interactions with an unstable one, while a pair of unstable EMEC waves yields an increased instability growth rate. Individually stable waves remain stable while interacting with one another. Stationary nonlinear solutions of the coupled equations are presented. The relevance of our investigation to nonlinear phenomena in space plasmas is discussed. (c) 2005 American Institute of Physics.

Modelling non-adiabatic processes using correlated electron-ion dynamics

Here we survey the theory and applications of a family of methods (correlated electron-ion dynamics, or CEID) that can be applied to a diverse range of problems involving the non-adiabatic exchange of energy between electrons and nuclei. The simplest method, which is a paradigm for the others, is Ehrenfest Dynamics. This is applied to radiation damage in metals and the evolution of excited states in conjugated polymers. It is unable to reproduce the correct heating of nuclei by current carrying electrons, so we introduce a moment expansion that allows us to restore the spontaneous emission of phonons. Because of the widespread use of Non-Equilibrium Green's Functions for computing electric currents in nanoscale systems, we present a comparison of this formalism with that of CEID with open boundaries. When there is strong coupling between electrons and nuclei, the moment expansion does not converge. We thus conclude with a reworking of the CEID formalism that converges systematically and in a stable manner.

Electron-phonon thermalization in a scalable method for real-time quantum dynamics

We present a quantum simulation method that follows the dynamics of out-of-equilibrium many-body systems of electrons and oscillators in real time. Its cost is linear in the number of oscillators and it can probe time scales from attoseconds to hundreds of picoseconds. Contrary to Ehrenfest dynamics, it can thermalize starting from a variety of initial conditions, including electronic population inversion. While an electronic temperature can be defined in terms of a nonequilibrium entropy, a Fermi-Dirac distribution in general emerges only after thermalization. These results can be used to construct a kinetic model of electron-phonon equilibration based on the explicit quantum dynamics.

Suprathermal electron flux peaks at stream interfaces: Signature of solar wind dynamics or tracer for open magnetic flux transport on the Sun?

The high variability of the intensity of suprathermal electron flux in the solar wind is usually ascribed to the high variability of sources on the Sun. Here we demonstrate that a substantial amount of the variability arises from peaks in stream interaction regions, where fast wind runs into slow wind and creates a pressure ridge at the interface. Superposed epoch analysis centered on stream interfaces in 26 interaction regions previously identified in Wind data reveal a twofold increase in 250 eV flux (integrated over pitch angle). Whether the peaks result from the compression there or are solar signatures of the coronal hole boundary, to which interfaces may map, is an open question. Suggestive of the latter, some cases show a displacement between the electron and magnetic field peaks at the interface. Since solar information is transmitted to 1 AU much more quickly by suprathermal electrons compared to convected plasma signatures, the displacement may imply a shift in the coronal hole boundary through transport of open magnetic flux via interchange reconnection. If so, however, the fact that displacements occur in both directions and that the electron and field peaks in the superposed epoch analysis are nearly coincident indicate that any systematic transport expected from differential solar rotation is overwhelmed by a random pattern, possibly owing to transport across a ragged coronal hole boundary.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Statistics and kinetics of single-molecule electron transfer dynamics in complex environments: A simulation model study

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)