The thermodynamics of mixing C6 and C7 compounds with a bicyclic compound at infinite dilution

The activity coefficients at infinite dilution have been measured at 25°C for cyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, benzene, n-hexane, 1-hexene, 1-hexyne, n-heptane, 1-heptene and 1-heptyne in decahydronaphthalene, bicyclohexyl, 1,2,3,4-tetrahydronaphthalene and cyclohexylbenzene. These results, together with previously determined H _m ^E and V _m ^E have been used to calculate the partial molar excess thermodynamic properties of mixing at infinite dilution.     

Determination of uranium in marine sediment pore waters by isotope dilution inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) was used in an isotope dilution mode to assay small-volume (0.25 ml) sediment pore waters for their uranium contents, using ²³⁶U as the spike. The only pretreatment required was a simple dilution by a factor of 20, which gave sufficient volume for three replicate analyses per sample. Rapid and accurate results were obtained for a variety of samples and standards, ranging in concentration from 0.05 to 10 ng U ml^?1. A suite of 30 samples can be analysed in less than 6 h by this method. The relative standard deviation was better than 1.9%, with a detection limit, based on 3σ background, of 2 pg U ml^?1 in solution (40 pg ml^?1 in samples). Sea water is a difficult matrix for ICP-MS and thus the method is generally suitable for uranium determinations in many other sample solutions.     

The crystal structure of carbamoyl fluoride,NH<Subscript>2</Subscript>COF

Although first synthesized in 1940, the X-ray crystal structure of carbamoyl fluoride, NH₂COF, has until now remained unknown. [1] NH₂COF crystallizes in the orthorhombic space group Ibam, is planar, and exhibits a short C-N bond length, 1.3168(13) Å, implying a significant degree of donation from the nitrogen lone pair. The structure features one molecule in the asymmetric unit and eight molecules in the unit cell. There are four molecules in two planar layers that are connected by a network of NH·O hydrogen bonds with N·O distances of 2.987(2) Å and 2.945(2) Å. The compound was also studied by quantum chemical calculations at both the ab initio (MP2) and density functional theory (B3LYP) level.     

On the choice of auxiliary linear operator in the optimal homotopy analysis of the Cahn-Hilliard initial value problem

Analytical solutions for the Cahn-Hilliard initial value problem are obtained through an application of the homotopy analysis method. While there exist numerical results in the literature for the Cahn-Hilliard equation, a nonlinear partial differential equation, the present results are completely analytical. In order to obtain accurate approximate analytical solutions, we consider multiple auxiliary linear operators, in order to find the best operator which permits accuracy after relatively few terms are calculated. We also select the convergence control parameter optimally, through the construction of an optimal control problem for the minimization of the accumulated L ²-norm of the residual errors. In this way, we obtain optimal homotopy analysis solutions for this complicated nonlinear initial value problem. A variety of initial conditions are selected, in order to fully demonstrate the range of solutions possible.     

Exact and analytical solutions for a nonlinear sigma model

We consider wave solutions to nonlinear sigma models in n dimensions. First, we reduce the system of governing PDEs into a system of ODEs through a traveling wave assumption. Under a new transform, we then reduce this system into a single nonlinear ODE. Making use of the method of homotopy analysis, we are able to construct approximate analytical solutions to this nonlinear ODE. We apply two distinct auxiliary linear operators and show that one of these permits solutions with lower residual error than the other. This demonstrates the effectiveness of properly selecting the auxiliary linear operator when performing homotopy analysis of a nonlinear problem. From here, we then obtain residual error‐minimizing values of the convergence control parameter. We find that properly selecting the convergence control parameter makes a drastic difference in the magnitude of the residual error. Together, appropriate selection of the auxiliary linear operator and of the convergence control parameter is shown to allow approximate solutions that quickly converge to the true solution, which means that few terms are needed in the construction of such solution. This, in turn, greatly improves computational efficiency. Copyright © 2013 John Wiley & Sons, Ltd.     

Conformational analysis of 1,1,2,2-tetraaryl-disilanes

A study of the static stereochemistry of 1,1,2,2-tetraphenyldisilane (1) and 1,1,2,2-tetramesityldisilane (2) by empirical force field calculations, X-ray diffraction, and ¹H NMR reveals that the preference for the anti conformation, exhibited by the unclamped 1,1,2,2-tetraarylethanes, is sustained in the analogous disilanes, although in somewhat attenuated form. This anti preference stands in contrast to the gauche preference of 1,1,2,2-tetraalkyldisilanes. Examination of ³J_HH coupling constants for R₂HSiSiHR₂; (R = phenyl, mesityl, 2,6-dimethyl-phenyl, t-butyl, cyclohexyl) suggests the existence of a Karplus relation for H-Si-Si-H systems.     

Vectorial Approach to Fast Correlation Attacks

A new, vectorial approach to fast correlation attacks on binary memoryless combiners is proposed. Instead of individual input sequences or their linear combinations, the new attack is targeting subsets of input sequences as a whole thus exploiting the full correlation between the chosen subset and the output sequence. In particular, the set of all the input sequences can be chosen as the target. The attack is based on a novel iterative probabilistic algorithm which is also applicable to general memoryless combiners over finite fields or finite rings. To illustrate the effectiveness of the introduced approach, experimental results obtained for random balanced combining functions are presentedMost of this work was done while he was with Rome CryptoDesign Center, Gemplus, Italy     

High-spin g factors and proton alignment in Pt

The average g factors of high-spin states in ^180,182,184Pt were measured by the transient-field technique. In all three isotopes the quasicontinuum g factor at an angular momentum of 20 is g0.37. This contrasts with similar measurements on other nuclei that have 70Z80, where typical values of g0.22 have been attributed to the influence of quasineutron alignments. Evidently proton and neutron configurations are about equally important at high spin in the Pt isotopes near mid-shell. This inference is consistent with the discrete spectroscopy, including the contention, supported by g_K−g_R values, that h_9/2 proton pairs align along with the i_13/2 neutrons at rotational frequencies of ω≈0.3 MeV in ¹⁸⁴Pt. Links between the quasicontinuum g factors and features in the discrete spectroscopy are explored by comparing and contrasting the behavior of ¹⁸⁴Pt and ¹⁶⁶Hf.     

The neural correlates of calculation ability in children: an fMRI study

Most studies investigating mental numerical processing involve adult participants and little is known about the functioning of these systems in children. The current study used functional magnetic resonance imaging (fMRI) to investigate the neural correlates of numeracy and the influence of age on these correlates with a group of adults and a group of third graders who had average to above average mathematical ability. Participants performed simple and complex versions of exact and approximate calculation tasks while in the magnet. Like adults, children activated a network of brain regions in the frontal and parietal lobes during the calculation tasks, and they recruited additional brain regions for the more complex versions of the tasks. However, direct comparisons between adults and children revealed significant differences in level of activation across all tasks. In particular, patterns of activation in the parietal lobe were significantly different as a function of age. Findings support previous claims that the parietal lobe becomes more specialized for arithmetic tasks with age.     

Derivation of the order parameter of the chiral Potts model

We derive the order parameter of the chiral Potts model, using the method of Jimbo et al. The result agrees with previous conjectures.