Ion-water clusters, bulk medium effects, and ion hydration

Thermochemistry of gas-phase ion-water clusters together with estimates of the hydration free energy of the clusters and the water ligands are used to calculate the hydration free energy of the ion. Often the hydration calculations use a continuum model of the solvent. The primitive quasichemical approximation to the quasichemical theory provides a transparent framework to anchor such efforts. Here we evaluate the approximations inherent in the primitive quasichemical approach and elucidate the different roles of the bulk medium. We find that the bulk medium can stabilize configurations of the cluster that are usually not observed in the gas phase, while also simultaneously lowering the excess chemical potential of the ion. This effect is more pronounced for soft ions. Since the coordination number that minimizes the excess chemical potential of the ion is identified as the optimal or most probable coordination number, for such soft ions, the optimum cluster size and the hydration thermodynamics obtained without account of the bulk medium on the ion-water clustering reaction can be different from those observed in simulations of the aqueous ion. The ideas presented in this work are expected to be relevant to experimental studies that translate thermochemistry of ion-water clusters to the thermodynamics of the hydrated ion and to evolving theoretical approaches that combine high-level calculations on clusters with coarse-grained models of the medium

Molecular packing and chemical association in liquid water simulated using ab initio hybrid Monte Carlo and different exchange-correlation functionals

In the free energy of hydration of a solute, the chemical contribution is given by the free energy required to expel water molecules from the coordination sphere and the packing contribution is given by the free energy required to create the solute-free coordination sphere (the observation volume) in bulk water. With the SPC/E water model as a reference, we examine the chemical and packing contributions in the free energy of water simulated using different electron density functionals. The density is fixed at a value corresponding to that for SPC/E water at a pressure of 1 bar. The chemical contribution shows that water simulated at 300 K with BLYP is somewhat more tightly bound than water simulated at 300 K with the revPBE functional or at 350 K with the BLYP and BLYP-D functionals. The packing contribution for various radii of the observation volume is studied. In the size range where the distribution of water molecules in the observation volume is expected to be Gaussian, the packing contribution is expected to scale with the volume of the observation sphere. Water simulated at 300 K with the revPBE and at 350 K with BLYP-D or BLYP conforms to this expectation, but the results suggest an earlier onset of system size effects in the BLYP 350 K and revPBE 300 K systems than that observed for either BLYP-D 350 K or SPC/E. The implication of this observation for constant pressure simulations is indicated. For water simulated at 300 K with BLYP, in the size range where Gaussian distribution of occupation is expected, we instead find non-Gaussian behavior, and the packing contribution scales with surface area of the observation volume, suggesting the presence of heterogeneities in the system

Micromegas TPC studies at high magnetic fields using the charge dispersion signal

The International Linear Collider (ILC) Time Projection Chamber (TPC) transverse space-point resolution goal is 100 microns for all tracks including stiff 90 degree tracks with the full 2 meter drift. A Micro Pattern Gas Detector (MPGD) readout TPC can achieve the target resolution with existing techniques using 1 mm or narrower pads at the expense of increased detector cost and complexity. The new MPGD readout technique of charge dispersion can achieve good resolution without resorting to narrow pads. This has been demonstrated previously for 2 mm x 6 mm pads with GEMs and Micromegas in cosmic ray tests and in a KEK beam test in a 1 Tesla magnet. We have recently tested a Micromegas-TPC using the charge dispersion readout concept in a high field super-conducting magnet at DESY. The measured Micromegas gain was found to be constant within 0.5% for magnetic fields up to 5 Tesla. With the strong suppression of transverse diffusion at high magnetic fields, we measure a flat 50 micron resolution at 5 Tesla over the full 15 cm drift length of our prototype TPC.Comment: 7 pages, 3 figure

Rate Determining Factors in Protein Model Structures

Previous research has shown a strong correlation of protein folding rates to the native state geometry, yet a complete explanation for this dependence is still lacking. Here we study the rate-geometry relationship with a simple statistical physics model, and focus on two classes of model geometries, representing ideal parallel and antiparallel structures. We find that the logarithm of the rate shows an almost perfect linear correlation with the "absolute contact order", but the slope depends on the particular class considered. We discuss these findings in the light of experimental results.Comment: 4 pages, 2 figure

Power in the Multinational Corporation in Industry Equilibrium

Recent theories of the multinational corporation introduce the property rights model of the firm and examine whether to integrate our outsource firm activities locally or to a foreign country. This paper focus instead on the internal organization of the multinational corporation by examining the power allocation between headquarters and subsidiaries. We provide a framework to analyse the interaction between the decision to serve the local market by exporting or FDI, market acces and the optimal mode of organization of the multinational corporation. We find that subsidiary managers are given most autonomy in their decision how to run the firm at intermediate levels of local competition. We then provide comparative statics for changes in fixed FDI entry costs and trade costs, information technology, the number of local competitors, and in the size of the local market

Accurate estimations of circumstellar and interstellar lines of quadruply ionized vanadium using the coupled cluster approach

Accurate {\it ab initio} calculations have been carried out to study the valence electron removal energies and oscillator strengths of astrophysically important electromagnetic transitions of quadruply ionized vanadium, $V^{4+}$. Many important electron correlations are considered to all-orders using the relativistic coupled-cluster theory. Calculated ionization potentials and fine structure splittings are compared with the experimental values, wherever available. To our knowledge, oscillator strengths of electric dipole transitions are predicted for the first time for most of the transitions. The transitions span in the range of ultraviolet, visible and near infrared regions and are important for astrophysical observations.Comment: Submitted in Astrophysical

Phycoremediation of Dairy Wastewater by Microalgae for elimination of organic pollution load

The present study aims to demonstrate the potential of microalgae Chlorococcum humicola for treatment of dairy industry effluent and reduction of its pollution load with the cultivation of microalgae in the same effluent. Dairy industry wastewater supplies the required nutrients for the growth of C. humicola and its growth was comparatively higher in 50 % dairy industry effluent as compare to Bold basal growth medium. Optimization of growth parameters of algae showed that growth of C. humicola was favoured by alkaline pH and optimum growth was observed at pH 8, whereas acidic pH does not favour the growth of selected algae. The exponential growth phase of C. humicola was achieved between 3-7 days, at 20˚C temperature, a further increase in temperature decreases the algal growth. The results for the effect of different concentration of dairy wastewater (0, 10, 25, 50, 75 and 100 %) on biochemical content (protein, chlorophyll a, carbohydrate) of C. humicola revealed that 50 % wastewater concentration was more efficient for enhancement of biochemical content of microalgae as compare to control. The result further showed considerable reduction in the organic pollution load of dairy wastewater as biological oxygen demand (BOD) and chemical oxygen demand (COD) reduced to 72 and 78 % respectively, after 15 days of treatment with C. humicola. The results also showed a reduction in the nutrient concentration of dairy wastewater such as nitrate, phosphate and sulphate by 92, 43, 62 % respectively, after 10 days of treatment and 96, 67 and 78 % respectively, after 15 days of microalgal treatment as compared to control (without microalgae). These findings suggested that dairy industry wastewater was a good nutrient supplement and can be directly used for mass cultivation of C. humicola without requiring additional nutrient supplements and also the microalgae C. humicola has a great potential for the treatment of dairy industry wastewate

Corporate Hierarchies and the Size of Nations: Theory and Evidence

Corporate organization varies within a country and across countries with country size. The paper starts by establishing some facts about corporate organization based on unique data of 660 Austrian and German corporations. The larger country (Germany) has larger firms with flatter more decentral corporate hierarchies compared to the smaller country (Austria). Firms in the larger country change their organization less fast than firms in the smaller country. Over time firms have been introducing less hierarchical organizations by delegating power to lower levels of the corporation. We develop a theory which explains these facts and which links these features to the trade environment that countries and firms face. We introduce firms with internal hierarchies in a Krugman (1980) model of trade. We show that international trade and the toughness of competition in international markets induce a power struggle in firms which eventually leads to decentralized corporate hierarchies. We offer econometric evidence which is consistent with the models predictions