Stability of O3 + N2, O3 + O2 and O3 + CO2 double hydrates: DFT study

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Existence and Stability for Spherical Crystals Growing in a Supersaturated Solution

We consider the growth of a spherical crystal in a supersaturatedsolution. In the first part, existence and uniqueness resultsfor radially symmetric growth are obtained, provided that thesupersaturation is not too large; conversely, when the far-fieldsupersaturation exceeds a critical value, it is shown that theradially symmetric solution ceases to exist in finite time.In the second part, we examine the linear stability of a radiallysymmetric similarity solution (in which the radius grows ast?) to shape perturbations. The results are compared with previousquasi-static analyses, and, in particular, the critical radiusat which the crystal becomes unstable is found to be largerfor small supersaturations, but smaller for large supersaturations,than those predicted by the quasi-static analysis     

Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.     

New ligands for the Fe(III)‐mediated reverse atom transfer radical polymerization of methyl methacrylate

A series of (di)picolinic acids and their derivates are investigated as novel complexing tridentate or bidentate ligands in the iron‐mediated reverse atom transfer radical polymerization of methyl methacrylate in N,N‐dimethylformamide at 100 °C with 2,2′‐azobisisobutyrontrile as an initiator. The polymerization rates and polydispersity indices (1.32–1.8) of the resulting polymers are dependent on the structures of the ligands employed. Different iron complexes may be involved in iron‐mediated reverse atom transfer radical polymerization, depending on the type of acid used. ¹H NMR spectroscopy has been used to study the structure of the resulting polymers. Chain‐extension reactions have been performed to further confirm the living nature of this catalytic system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2912–2921, 2006     

Dependence of the H2-H2 Interaction on the Monomer Bond Lengths: Steps Toward an Accurate ab initio Estimate

We compute the vibrational coupling between two H₂ molecules from ab initio quantum chemical calculations of the H₂-H₂ potential carried out at the full configuration interaction level of theory using the atom-centered aug-cc-pVTZ basis set for hydrogen. We compare the full configuration interaction results with those obtained using two variants of coupled cluster theory and find that a fully iterative treatment of connected triples may be required to estimate the H₂-H₂ vibrational coupling accurately using coupled cluster theory.     

AGE method simulations of a turbulent far‐wake compared to spectral DNS

Turbulent flow simulation methods based on finite differences are attractive for their simplicity, flexibility and efficiency, but not always for accuracy or stability. This paper demonstrates that a good compromise is possible with the advected grid explicit (AGE) method. Starting from the same initial field as a previous spectral DNS, AGE method simulations of a planar turbulent wake were carried out as DNS, and then at three levels of reduced resolution. The latter cases were in a sense large‐eddy simulations (LES), although no specific sub‐grid‐scale model was used. Results for the two DNS methods, including variances and power spectra, were very similar, but the AGE simulation required much less computational effort. Small‐scale information was lost in the reduced resolution runs, but large‐scale mean and instantaneous properties were reproduced quite well, with further large reductions in computational effort. Quality of results becomes more sensitive to the value chosen for one of the AGE method parameters as resolution is reduced, from which it is inferred that the numerical stability procedure controlled by the parameter is acting in part as a sub‐grid‐scale model. Copyright © 2002 John Wiley & Sons, Ltd.     

Numerical solutions of the shallow water equations with discontinuous bed topography

A simple scheme is developed for treatment of vertical bed topography in shallow water flows. The effect of the vertical step on flows is modelled with the shallow water equations including local energy loss terms. The bed elevation is denoted with z_b^‐ for the left and z_b⁺ for the right values at each grid point, hence exactly representing a discontinuity in the bed topography. The surface gradient method (SGM) is generalized to reconstruct water depths at cell interfaces involving a vertical step so that the fluxes at the cell interfaces can accurately be calculated with a Riemann solver. The scheme is verified by predicting a surge crossing a step, a tidal flow over a step and dam‐break flows on wet/dry beds. The results have shown good agreements compared with analytical solutions and available experimental data. The scheme is efficient, robust, and may be used for practical flow calculations. Copyright © 2002 John Wiley & Sons, Ltd.     

OPTIMAL INVESTMENT IN THE PROTECTION OF A VULNERABLE BIOLOGICAL RESOURCE

It is assumed that the probability of destruction of a biological asset by natural hazards can be reduced through investment in protection. Specifically a model, in which the hazard rate depends on both the age of the asset and the accumulated invested protection capital, is assumed. The protection capital depreciates through time and its effectiveness in reducing the hazard rate is subject to diminishing returns. It is shown how the investment schedule to maximize the expected net present value of the asset can be determined using the methods of deterministic optimal control, with the survival probability regarded as a state variable. The optimal investment pattern involves “bang-bang-singular” control. A numerical scheme for determining jointly the optimal investment policy and the optimal harvest (or replacement) age is outlined and a numerical example involving forest fire protection is given.