Clusters energy diffusion

Fig. 15. Cluster network model for highly cation-permselective Nafion membranes126). Counterions are largely concentrated in the high-charge shaded regions which provide somewhat tortuous, but continuous (low activation energy), diffusion pathways. Coions are largely confined to the central cluster regions and must, therefore, overcome a high electrical barrier, in order to diffuse from one cluster to the next...

Before carrying out the energy diffusion calculations on the water cluster, it is useful to determine the speed of sound in glassy water, which we compute from the dispersion relation for the water cluster. To compute a dispersion relation, we need to assign a wave number, k, to a normal mode of frequency, go. We have obtained dispersion relations for proteins [111] via computation of the correlation function for the direction of atomic displacements as a function of distance for individual normal modes of the protein, a function that was studied in earlier work by Nishikawa and Go [112], Computation of the correlation function allows us to match a wave number of a plane wave to a normal mode... 

In the second part of the chapter, we have examined the spread of vibrational energy through coordinate space in systems that are large on the molecular scale—in particular, clusters of hundreds of water molecules and proteins—and computed thermal transport coefficients for these systems. The coefficient of thermal conductivity is given by the product of the heat capacity per unit volume and the energy diffusion coefficient summed over all vibrational modes. For the water clusters, the frequency-dependent energy diffusion coefficient was... 

First we look at the simpler case of the shrinking of a single cluster of radius R at two-phase coexistence. Assume that the phase inside this cluster and the surrounding phase are at thermodynamic equilibrium, apart from the surface tension associated with the cluster surface. This surface tension exerts a force or pressure inside the cluster, which makes the cluster energetically unfavorable so that it shrinks, under diffusive release of the conserved quantity (matter or energy) associated with the order parameter. 

We now describe a relatively simple MD model of a low-index crystal surface, which was conceived for the purpose of studying the rate of mass transport (8). The effect of temperature on surface transport involves several competing processes. A rough surface structure complicates the trajectories somewhat, and the diffusion of clusters of atoms must be considered. In order to simplify the model as much as possible, but retain the essential dynamics of the mobile atoms, we will consider a model in which the atoms move on a "substrate" represented by an analytic potential energy function that is adjusted to match that of a surface of a (100) face-centered cubic crystal composed of atoms interacting with a Lennard-Jones... 

Room temperature deposition of silver on Pd(lOO) produces a rather sharp Ag/Pd interface [62]. The interaction with a palladium surface induces a shift of Ag 3d core levels to lower binding energies (up to 0.7 eV) while the Pd 3d level BE, is virtually unchanged. In the same time silver deposition alters the palladium valence band already at small silver coverage. Annealing of the Ag/Pd system at 520 K induces inter-diffusion of Ag and Pd atoms at all silver coverage. In the case when silver multilayer was deposited on the palladium surface, the layered silver transforms into a clustered structure slightly enriched with Pd atoms. A hybridization of the localized Pd 4d level and the silver sp-band produces virtual bound state at 2eV below the Fermi level. 

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