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

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.

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

Water exchange at a hydrated platinum electrode is rare and collective

We use molecular dynamics simulations to study the exchange kinetics of water molecules at a model metal electrode surface -- exchange between water molecules in the bulk liquid and water molecules bound to the metal. This process is a rare event, with a mean residence time of a bound water of about 40 ns for the model we consider. With analysis borrowed from the techniques of rare-event sampling, we show how this exchange or desorption is controlled by (1) reorganization of the hydrogen bond network within the adlayer of bound water molecules, and by (2) interfacial density fluctuations of the bulk liquid adjacent to the adlayer. We define collective coordinates that describe the desorption mechanism. Spatial and temporal correlations associated with a single event extend over nanometers and tens of picoseconds.Comment: 10 pages, 9 figure

Enhancement of the Curie temperature in GaMnAs/InGaMnAs superlattices

We report on an enhancement of the Curie temperature in GaMnAs/InGaMnAs superlattices grown by low-temperature molecular beam epitaxy, which is due to thin InGaMnAs or InGaAs films embedded into the GaMnAs layers. The pronounced increase of the Curie temperature is strongly correlated to the In concentration in the embedded layers. Curie temperatures up to 110 K are observed in such structures compared to 60 K in GaMnAs single layers grown under the same conditions. A further increase in T$_C$ up to 130 K can be achieved using post-growth annealing at temperatures near the growth temperature. Pronounced thickness fringes in the high resolution X-ray diffraction spectra indicate good crystalline quality and sharp interfaces in the structures.Comment: 4 pages, 4 figures, submitted to Appl. Phys. Let