Microscopic dynamics of charge separation at the aqueous electrochemical interface

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water-metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali-halide pair, Na$^+$I$^-$, or classical ions, and the products of water autoionization, H$_3$O$^+$OH$^-$, or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water's collective role in the process, is conserved between the bulk liquid and the electrode interface. Despite this, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free energy barrier to charge separation and a smaller flux over that barrier at the interface, results in a rate of dissociation that is 40x slower relative to the bulk. For water ions, a slightly higher free energy barrier is offset by a higher flux over the barrier from longer lived hydrogen bonding patters at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface.Comment: 6 pages, 3 figures + S

Electronic and magnetic properties of GaMnAs: Annealing effects

The effect of short-time and long-time annealing at 250C on the conductivity, hole density, and Curie temperature of GaMnAs single layers and GaMnAs/InGaMnAs heterostructures is studied by in-situ conductivity measurements as well as Raman and SQUID measurements before and after annealing. Whereas the conductivity monotonously increases with increasing annealing time, the hole density and the Curie temperature show a saturation after annealing for 30 minutes. The incorporation of thin InGaMnAs layers drastically enhances the Curie temperature of the GaMnAs layers.Comment: 4 pages, 6 figures, submitted to Physica

Characterizing heterogeneous dynamics at hydrated electrode surfaces

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this adlayer dynamic heterogeneity responds asymmetrically to applied voltage.Comment: 6 page, 4 figure

Effect of annealing on the depth profile of hole concentration in (Ga,Mn)As

The effect of annealing at 250 C on the carrier depth profile, Mn distribution, electrical conductivity, and Curie temperature of (Ga,Mn)As layers with thicknesses > 200 nm, grown by molecular-beam epitaxy at low temperatures, is studied by a variety of analytical methods. The vertical gradient in hole concentration, revealed by electrochemical capacitance-voltage profiling, is shown to play a key role in the understanding of conductivity and magnetization data. The gradient, basically already present in as-grown samples, is strongly influenced by post-growth annealing. From secondary ion mass spectroscopy it can be concluded that, at least in thick layers, the change in carrier depth profile and thus in conductivity is not primarily due to out-diffusion of Mn interstitials during annealing. Two alternative possible models are discussed.Comment: 8 pages, 8 figures, to appear in Phys. Rev.

Charge fluctuations in nano-scale capacitors

The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers in particular an efficient, accurate and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes, and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid