Molecular-dynamics analysis of the diffusion of molecular hydrogen in all-silica sodalite

In order to investigate the technical feasibility of crystalline porous silicates as hydrogen storage materials, the self-diffusion of molecular hydrogen in all-silica sodalite is modeled using large-scale classical molecular-dynamics simulations employing full lattice flexibility. In the temperature range of 700-1200 K, the diffusion coefficient is found to range from 1.610(-10) to 1.810(-9) m(2)/s. The energy barrier for hydrogen diffusion is determined from the simulations allowing the application of transition state theory, which, together with the finding that the pre-exponential factor in the Arrhenius-type equation for the hopping rate is temperature-independent, enables extrapolation of our results to lower temperatures. Estimates based on mass penetration theory calculations indicate a promising hydrogen uptake rate at 573 K.     

Confocal microscopy of a dense particle system

We report experiments utilizing confocal microscopy to determine the position of cornflour starch granules in a paste, as a function of distance from a wall. The granules have an average diameter of 15 mum. If a solvent is chosen such as to approximately match the refractive index of the granules then images of them can be obtained to a depth of 120 mum, which is the limit imposed by the working distance of the x 40 oil immersion lens used in the experiment. An algorithm is presented which successfully identifies the particle centers in 3D. In addition to experiments on static systems we show how measurements of particle number density and velocity can be obtained from images of a system in pipe flow. We find that particles are depleted from the wall over a range of around 100 mum.     

Ueber die Bestimmung des Cadmiums

Ohne Zusammenfassung     

Low reactivity of non-bridging oxygen defects on stoichiometric silica surfaces

Using ab initio molecular dynamics simulations we demonstrate that surfaces of stoichiometric silica exhibiting non-bridging oxygen defects can be surprisingly resistant to attack by water.     

Dependence of charge transfer reorganization energy on carrier localisation in organic molecular crystals

Taking the organic molecular material dithiophene-tetrathiafulvalene (DT-TTF) as an example of a high mobility organic molecular material, we use density functional calculations to calculate the dependency of the reorganization energy associated with charge carrier transport on: (i) the geometric and electronic responsiveness of the local molecular crystal environment, and, (ii) the local spatial extent of the charge carrier. We find that in our most realistic extended models the charge transfer reorganization energy is strongly dependent on carrier localization. In particular, whereas highly localized carriers are found to be highly susceptible to their charge transfer efficiency being affected by changes in the local crystal environment, more delocalized carriers are better able to maintain their low reorganization energies. Considering that maintaining a relatively small charge transfer reorganization energy magnitude is an important factor in achieving high carrier mobilities, we suggest that those materials better able to sustain carriers with short-range thermally resistant intermolecular delocalisation should be sought for device applications.     

Influence of intermolecular interactions on the formation of tetra(carbomethoxy)-tetrathiafulvalene assemblies.

We study the assemblies that tetra(carbomethoxy)tetrathiafulvalene (TCM-TTF) forms in solution and when deposited on a surface depending on intermolecular interactions and on the interactions with the substrate and the solvent. Its organization on graphite and mica substrates was studied by atomic force microscopy, and different molecular assemblies were observed depending on the prevailing interactions. The promotion of molecule-molecule interactions gave rise to the formation of molecular fibers. The investigation of the influence of the solvent-molecule interactions on TCM-TTF molecular organizations was carried out by UV/Vis spectroscopy, and a new TCM-TTF polymorph was obtained by changing the nature of the solvent. Finally, an explanation for all these phenomena, supported by computational modeling, is put forward.     

Molecular dynamics-based approach to study the anisotropic self-diffusion of molecules in porous materials with multiple cage types: application to H2 in losod

The anisotropic self-diffusion of molecular hydrogen in the multiple cage clathrasil losod (LOS) is modeled by means of molecular dynamics (MD) simulations of up to 1 micros for the temperature range 900-1200 K while treating the framework as fully flexible. The LOS diffusion tensor is calculated employing an analytical method based on hopping rates. The diffusion in the c-direction of the unit cell is found to be approximately two times more rapid than in the a- and the b-directions, a characteristic of importance for the application of LOS as a membrane. The overall diffusion is based on five different hop types for which the individual hopping rates and diffusion barriers are calculated separately. We show explicitly that the shape and volume of the cages have a significant effect on the hopping rates and further that even small deformations of the circular Si6O6 apertures have a large influence on the energetic barrier for hydrogen diffusion. Compared to the single cage clathrasils dodecasil 3C (MTN) and sodalite (SOD), LOS has a lower diffusion rate. However, from a technical point of view this rate (at 573 K) is still fast enough for LOS to be interesting as a size-selective membrane or as a hydrogen-adsorption medium.