The optimal P3M algorithm for computing electrostatic energies in periodic systems

We optimize Hockney and Eastwood's particle-particle particle-mesh algorithm to achieve maximal accuracy in the electrostatic energies (instead of forces) in three-dimensional periodic charged systems. To this end we construct an optimal influence function that minimizes the root-mean-square (rms) errors of the energies. As a by-product we derive a new real-space cutoff correction term, give a transparent derivation of the systematic errors in terms of Madelung energies, and provide an accurate analytical estimate for the rms error of the energies. This error estimate is a useful indicator of the accuracy of the computed energies and allows an easy and precise determination of the optimal values of the various parameters in the algorithm (Ewald splitting parameter, mesh size, and charge assignment order).     

Hamiltonians on discrete structures: jumps of the integrated density of states and uniform convergence

We study equivariant families of discrete Hamiltonians on amenable geometries and their integrated density of states (IDS). We prove that the eigenspace of a fixed energy is spanned by eigenfunctions with compact support. The size of a jump of the IDS is consequently given by the equivariant dimension of the subspace spanned by such eigenfunctions. From this we deduce uniform convergence (w.r.t. the spectral parameter) of the finite volume approximants of the IDS. Our framework includes quasiperiodic operators on Delone sets, periodic and random operators on quasi-transitive graphs, and operators on percolation graphs.     

Oxygen-tolerant [NiFe]-hydrogenases: the individual and collective importance of supernumerary cysteines at the proximal Fe-S cluster

An important clue to the mechanism for O(2) tolerance of certain [NiFe]-hydrogenases is the conserved presence of a modified environment around the iron-sulfur cluster that is proximal to the active site. The O(2)-tolerant enzymes contain two cysteines, located at opposite ends of this cluster, which are glycines in their O(2)-sensitive counterparts. The strong correlation highlights special importance for electron-transfer activity in the protection mechanism used to combat O(2). Site-directed mutagenesis has been carried out on Escherichia coli hydrogenase-1 to substitute these cysteines (C19 and C120) individually and collectively for glycines, and the effects of each replacement have been determined using protein film electrochemistry and electron paramagnetic resonance (EPR) spectroscopy. The "split" iron-sulfur cluster EPR signal thus far observed when oxygen-tolerant [NiFe]-hydrogenases are subjected to oxidizing potentials is found not to provide any simple, reliable correlation with oxygen tolerance. Oxygen tolerance is largely conferred by a single cysteine (C19), replacement of which by glycine removes the ability to function even in 1% O(2).     

The dissociative adsorption of hydrogen on Pt(111): actuation and acceleration by atomic defects

The dissociation of hydrogen at atomic surface defects is the strongly dominant, if not the decisive, step in the chain of events eventually leading to chemisorbed H-atoms on Pt(111). This holds for perpendicular kinetic energies of the gas phase molecules from 8 to 60 meV, i.e., covering the range relevant to hydrogenation reactions. This insight has been gained in the present study in which we reversibly varied the defect density on one and the same crystal in a controlled way. Information has been derived from measuring the adsorption kinetics as a function of coverage. Two distinct adsorption channels are distinguished. The first, indirect one, prevails at lower H-coverage and involves capture into a non-accommodated molecular precursor state followed by dissociation at step sites as described in our recent paper. The second one, dominant at higher coverage and non-negligible defect densities, obeys second order Langmuir kinetics. Here the dissociative adsorption takes place directly at step sites with a cross section of 0.24 unit cells (initial sticking probability 24% of the step density). These results are consistent with thermally programmed desorption data: the direct channel is responsible for the emergence of the low temperature peak in thermal desorption spectroscopy, usually denoted with β(1), while the indirect channel is represented by the β(2) state. The dependence on the perpendicular component of the hydrogen kinetic energy is distinctly different for the two channels: the indirect one shows power law behavior with an exponent 1.9 ± 0.1, while the direct one shows no perpendicular energy dependence at all.     

Study of the local SOC distribution in a lithium-ion battery by physical and electrochemical modeling and simulation

In this work a two-dimensional physical and electrochemical model of a lithium-ion secondary battery is presented. The transport processes and charge transfer reactions in a five layered single cell consisting of current collectors, electrode layers and separator are described by a system of partial differential equations which is solved with Comsol Multiphysics^®, a modeling and simulation tool based on the finite element method. Model validation with experimental discharge characteristics of a _{LiNi1/3Mn1/3Co1/3O2}/_C6${\mathit{LiNi}}_{1/3}{\mathit{Mn}}_{1/3}{\mathit{Co}}_{1/3}{O}_2/C_6$ cell at current rates of 1C to 5C was conducted and precious findings about the local state of charge of the intercalation material in dependence of its distance to the separator and the size of the active particles were made and could be explained in detail.     

Light-driven hydrogen production by a hybrid complex of a [NiFe]-hydrogenase and the cyanobacterial photosystem I

In order to generate renewable and clean fuels, increasing efforts are focused on the exploitation of photosynthetic microorganisms for the production of molecular hydrogen from water and light. In this study we engineered a 'hard-wired' protein complex consisting of a hydrogenase and photosystem I (hydrogenase-PSI complex) as a direct light-to-hydrogen conversion system. The key component was an artificial fusion protein composed of the membrane-bound [NiFe] hydrogenase from the beta-proteobacterium Ralstonia eutropha H16 and the peripheral PSI subunit PsaE of the cyanobacterium Thermosynechococcus elongatus. The resulting hydrogenase-PsaE fusion protein associated with PsaE-free PSI spontaneously, thereby forming a hydrogenase-PSI complex as confirmed by sucrose-gradient ultracentrifuge and immunoblot analysis. The hydrogenase-PSI complex displayed light-driven hydrogen production at a rate of 0.58 mumol H(2).mg chlorophyll(-1).h(-1). The complex maintained its accessibility to the native electron acceptor ferredoxin. This study provides the first example of a light-driven enzymatic reaction by an artificial complex between a redox enzyme and photosystem I and represents an important step on the way to design a photosynthetic organism that efficiently converts solar energy and water into hydrogen.     

Absolutely continuous spectrum for random operators on trees of finite cone type

We study the spectrum of random operators on a large class of trees. These trees have finitely many cone types and they can be constructed by a substitution rule. The random operators are perturbations of Laplace type operators either by random potentials or by random hopping terms, i.e., perturbations of the off-diagonal elements. We prove stability of arbitrary large parts of the absolutely continuous spectrum for sufficiently small but extensive disorder.