Diffusion von Dotierungsmaterial in Silizium

Ohne Zusammenfassung     

Sampling of rare events using hidden restraints

A method to enhance sampling of rare events is presented. It makes use of distance or dihedral-angle restraints to overcome an energy barrier separating two metastable states or to stabilize a transition state between the two metastable states. In order not to perturb these metastable end states themselves, a prefactor is introduced into the restraining energy function, which smoothly increases the weight of this function from zero to one at the transition state or on top of the separating energy barrier and then decreases the weight again to zero at the final state. The method is combined with multi-configurational thermodynamic integration and applied to two biomolecular systems, which were difficult to treat using standard thermodynamic integration. As first example the free energy difference of a cyclic alpha-aminoxy-hexapeptide-ion complex upon changing the ion from Cl- to Na+ was calculated. A large conformational rearrangement of the peptide was necessary to accommodate this change. Stabilizing the transition state by (hidden) restraints facilitates that. As a second example, the free energy difference between the 4C1 and the 1C4 conformation of beta-D-glucopyranoside was calculated. In unrestrained simulations the change from the 4C1 into the 1C4 conformation was never observed because of the high energy barrier separating the two states. Using (hidden) restraints, the transition from the 4C1 into the 1C4 state and back could be enforced without perturbing the end states. As comparison, for the same transitions the potential of mean force as obtained by using dihedral-angle constraints is provided.     

Propensity for the air/water interface and ion pairing in magnesium acetate vs magnesium nitrate solutions: molecular dynamics simulations and surface tension measurements

Molecular dynamics simulations in slab geometry and surface tension measurements were performed for aqueous solutions of magnesium acetate and magnesium nitrate at various concentrations. The simulations reveal a strong affinity of acetate anions for the surface, while nitrate exhibits only a very weak surface propensity, and magnesium is per se strongly repelled from the air/water interface. CH3COO- also exhibits a much stronger tendency than NO3- for ion pairing with Mg2+ in the bulk and particularly in the interfacial layer. The different interfacial behavior of the two anions is reflected by the opposite concentration dependence (beyond 0.5 M) of surface tension of the corresponding magnesium salts. Measurements, supported by simulations, show that the surface tension of Mg(NO3)2(aq) increases with concentration as for other inorganic salts. However, in the case of Mg(OAc)2(aq) the surface tension isotherm exhibits a turnover around 0.5 M, after which it starts to decrease, indicating a positive net solute excess in the interfacial layer at higher concentrations.     

Orbits in the field of a gravitating magnetic monopole

Orbits of test particles and light rays are an important tool to study the properties of space-time metrics. Here we systematically study the properties of the gravitational field of a globally regular magnetic monopole in terms of the geodesics of test particles and light. The gravitational field depends on two dimensionless parameters, defined as ratios of the characteristic mass scales present. For critical values of these parameters the resulting metric coefficients develop a singular behavior, which has profound influence on the properties of the resulting space-time and which is clearly reflected in the orbits of the test particles and light rays.     

Stationary Dyonic regular and black hole solutions

We consider globally regular and black hole solutions in SU(2) Einstein–Yang–Mills–Higgs theory, coupled to a dilaton field. The basic solutions represent magnetic monopoles, monopole–antimonopole systems or black holes with monopole or dipole hair. When the globally regular solutions carry additionally electric charge, an angular momentum density results, except in the simplest spherically symmetric case. We evaluate the global charges of the solutions and their effective action, and analyze their dependence on the gravitational coupling strength. We show, that in the presence of a dilaton field, the black hole solutions satisfy a generalized Smarr type mass formula. B. Kleihaus gratefully acknowledges support by the German Aerospace Center. F. Navarro-Lérida gratefully acknowledges support by the Ministerio de Educación y Ciencia under grant EX2005-0078.     

Synthesis and Characterization of Ligand-Linked Pt Nanoparticles: Tunable,Three-Dimensional,Porous Networks for Catalytic Hydrogen Sensing

Porous networks of Pt nanoparticles interlinked by bifunctional organic ligands have shown high potential as catalysts in micro-machined hydrogen gas sensors. By varying the ligand among p-phenylenediamine, benzidine, 4,4‘‘-diamino-p-terphenyl, 1,5-diaminonaphthalene, and trans-1,4-diaminocyclohexane, new variants of such networks were synthesized. Inter-particle distances within the networks, determined via transmission electron microscopy tomography, varied from 0.8 to 1.4 nm in accordance with the nominal length of the respective ligand. While stable structures with intact and coordinatively bonded diamines were formed with all ligands, aromatic diamines showed superior thermal stability. The networks exhibited mesoporous structures depending on ligand and synthesis strategy and performed well as catalysts in hydrogen gas microsensors. They demonstrate the possibility of deliberately tuning micro- and mesoporosity and thereby transport properties and steric demands by choice of the right ligand also for other applications in heterogeneous catalysis.     

Thermodynamic Properties of <Emphasis Type="SmallCaps">l</Emphasis>-Aspartates of Alkali and Alkali-Earth Metals in Aqueous Solutions at 298.15 and 310.15 K and Specific Cation Effects on Biomolecule Solvation

Vapor pressure osmometry was applied to the systems calcium l-aspartate ((S)-aminobutanedioic acid calcium salt)?+?water for varying molalities of Ca–l-Asp (m_Ca–l-Asp?=?0.01–1.02 mol·kg^?1) and guanidinium hydrochloride (methanamidine hydrochloride)?+?sodium L–aspartate ((S)–aminobutanedioic acid sodium salt)?+?water, varying the molalities of GndmCl and Na–l-Asp (m_Na–l-Asp?=?0.1, 0.25, 0.4, 0.57 mol·kg^?1 and m_GndmCl?=?0.1–1.1 mol·kg^?1) at T?=?298.15 K and 310.15 K. From vapor pressure osmometry, activities of water, and the corresponding osmotic coefficients of the mixtures Ca–l-Asp?+?water and Na–l-Asp?+?GndmCl?+?water have been calculated, both being directly related to the chemical potentials of the different species and therefore to their Gibbs energy. Mean molal ion activity coefficients were obtained from experimental data fits with the Pitzer equations and the corresponding dual and triple interaction parameters were derived for the Ca–l-Asp?+?water binary system. β⁽²⁾ Pitzer parameters different from zero are required for Ca–l-Asp in water to reproduce the osmotic coefficient decrease with increasing concentration. Mean Spherical Approximation parameters accounting for Coulomb and short range interactions that describe the calcium and magnesium aspartates and glutamates are given. The decrease in the chemical potential of the aspartates corresponds to the Hofmeister series: NaAsp?>?Mg(Asp)₂?>?CaAsp. A strong interaction between amino acid and salt due to specific dispersion interactions in amino acid salt systems containing guanidinium based salt has been revealed that is in agreement with MD and half-empirical quantum-chemical calculations.     

Qualitative Analyse von Kationen

Analytical and Bioanalytical Chemistry -