Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide

Using FTIR and Raman spectroscopy, the formation of halogen bonded complexes of the trifluorohalomethanes CF(3)Cl, CF(3)Br and CF(3)I with dimethyl sulfide (DMS) dissolved in liquid krypton has been investigated. For CF(3)Br and CF(3)I, evidence was found for the formation of C-XS halogen bonded 1:1 complexes. At higher concentrations of CF(3)I weak absorptions due to a 2:1 complex were also observed. Using spectra recorded at temperatures between 118 and 163 K, the complexation enthalpies for the complexes were determined to be -9.5(5) kJ mol(-1) for CF(3)Br·DMS, -17.4(1) kJ mol(-1) for CF(3)I·DMS and -30.8(16) kJ mol(-1) for (CF(3)I·)(2)DMS. The results from the cryospectroscopic study are compared with ab initio calculations at the MP2/aug-cc-pVDZ(-PP) level. Apart from vibrational modes localized in the trifluorohalomethanes and the DMS moieties, for both CF(3)Br and CF(3)I, an additional band, which we assign as the intermolecular stretching mode in the complex, was identified in the infrared and Raman spectra.     

Composing dinatural transformations: Towards a calculus of substitution

Dinatural transformations, which generalise the ubiquitous natural transformations to the case where the domain and codomain functors are of mixed variance, fail to compose in general; this has been known since they were discovered by Dubuc and Street in 1970. Many ad hoc solutions to this remarkable shortcoming have been found, but a general theory of compositionality was missing until Petri?, in 2003, introduced the concept of g-dinatural transformations, that is, dinatural transformations together with an appropriate graph: he showed how acyclicity of the composite graph of two arbitrary dinatural transformations is a sufficient and essentially necessary condition for the composite transformation to be in turn dinatural. Here we propose an alternative, semantic rather than syntactic, proof of Petri?'s theorem, which the authors independently rediscovered with no knowledge of its prior existence; we then use it to define a generalised functor category, whose objects are functors of mixed variance in many variables, and whose morphisms are transformations that happen to be dinatural only in some of their variables.We also define a notion of horizontal composition for dinatural transformations, extending the well-known version for natural transformations, and prove it is associative and unitary. Horizontal composition embodies substitution of functors into transformations and vice-versa, and is intuitively reflected from the string-diagram point of view by substitution of graphs into graphs.This work represents the first, fundamental steps towards a substitution calculus for dinatural transformations as sought originally by Kelly, with the intention then to apply it to describe coherence problems abstractly. There are still fundamental difficulties that are yet to be overcome in order to achieve such a calculus, and these will be the subject of future work; however, our contribution places us well in track on the path traced by Kelly towards a calculus of substitution for dinatural transformations.     

Laboratory simulation of inertial and frictional effects on barotropic rotating flows over and past obstacles: Comparison with simple numerical and analytical models

Summary This paper presents the results of laboratory experiments designed to simulate some basic process of large-scale flows interacting with obstacles, also in order to better understand details of subsynoptic disturbances that are created in the lee of large topographic features. For this event, the experimental facilities of the Istituto di Cosmogeofisica of Consiglio Nazionale delle Ricerche (CNR) were exploited, consisting in a hydraulic channel mounted on a rotating platform, along whose longitudinal axis a hemispherical obstacle was towed at various speeds. Because of the conversion of potential vorticity, the experimental results showed, as expected, the existence of a region of anticyclonic circulation, located above the obstacle; however, also an asymmetric pattern of positive vorticity located downwind of the obstacle did appear, which cannot be interpreted in terms of simple quasi-geostrophic inviscid dynamics. This behaviour is not surprising, if one considers that the real flow near the obstacle could hardly ever match the conditions of inviscid quasi-geostrophy (Ro≪1,E∼0), but was similar to that characterising the zone close to the surface of the obstacle, where inertial and viscous effects are not negligible. Finally, in order to investigate the importance of these effects on the interaction processes, simple numerical and analytical models were applied, by which the consistency of some laboratory simulations, chosen among the most significant ones, could be compared.     

Hydraulic simulation of negatively buoyant plumes

Summary The results of a hydraulic simulation of denser-than-air plumes in a neutral atmosphere are presented and discussed. The behaviour of these amission is of particular practical interest in connection with problems of geothermal drilling. The experimental data, concerning the height and the horizontal distance from the source of the maximum plume rise, as well as the distance where the plume touches ground, were compared with simple analytical formulae available in the literature. It was found that plume rise is described with sufficient accuracy by Meroney's model; for touchdown distance an empirical formula, obtained fitting the data from the present experiment, is proposed. It was seen, moreover, that in the examined range of variability of the emission parameters the best value to be adopted for the entrainment coefficient is β=0.4.

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Riassunto Si presentano e discutono i risultati di uno studio in vasca idraulica del comportamento in atmosfera neutra di getti piú densi dell'aria, di particolare interesse in relazione a problemi di perforazione di pozzi geotermici. I dati sperimentali, riguardanti il massimo sovrainnalzamento dei pennacchi, la distanza orizzontale dalla ciminiera a cui tale massimo viene raggiunto, nonché la distanza alla quale il pennacchio ricade al suolo, sono stati confrontati con semplici formule analitiche reperibili in letteratura. Si è trovato che il ?plume rise? è descritto con sufficiente accuratezza dal modello di Meroney, mentre per la distanza di ricaduta si propone una formula empirica ottenuta per interpolazione dei dati di questo esperimento. Si è visto inoltre che nell'intervallo qui esaminato di variabilità dei parametri di emissione il valore piú opportuno da assegnare al coefficiente di ?entrainment? à β=0.4.

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Theoretical and experimental power spectra of neutron monitor time series in 1978

Summary A comprehensive model for the spectral analysis of neutron monitor data is presented. The contributions to the power spectrum include scintillations in the interplanetary magnetic field caused by cosmic-ray diffusion along and perpendicularly to the field and Forbush-decrease effects. The effects of the Earth's rotation and of nonlinear interactions between particles and fields are taken into account. The model is then compared with the 1978 data of the ?polar? station of Alert and the ?quasi-equatorial? station of Deep River and the agreement is very satisfactory.

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Riassunto Si presenta un modello generale per l'analisi spettrale dei dati da monitori di neutroni. I contributi allo spettro di potenza includono le scintillazioni nel campo magnetico interplanetario dovute alla diffusione dei raggi cosmici lungo il campo e perpendicolarmente ad esso e gli effetti delle diminuzioni Forbush. Si considerano anche gli effetti della rotazione della Terra e delle interazioni non lineari fra particelle e campi. Il modello è quindi confrontato con i dati 1978 della stazione ?polare? di Alert e di quella ?quasi equatoriale? di Deep River e l'accordo risulta molto soddisfacente.

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Резюме Предлагается общая модель для спектрального анализа данных с нейтронных мониторов. Вклады в степенной спектр включают сцинтилляции в межпланетном магнитном поле, обусловленние диффузией космуческих лучей вдоль и перпендикулярно полю и эффектами ?уменьшений? форбуша. Учитываются эффекты вращения Земли и нелинейных взаимодействий между частицами и полями. Затем предложенная модель сравнивается с данными, полученными в 1978 г. на ?полярной? станции Алерт и на ?квазиэкваториальной? станции Дип Ривер. Получено удовлетворительное согласие.

     

Evolution of the Pt layer deposited on MgO(001) by pulsed laser deposition as a function of the deposition parameters: a scanning tunneling microscopy and energy dispersive X-ray diffractometry/reflectometry study

A combined ultrahigh vacuum scanning tunneling microscopy (STM-UHV) and energy dispersive X-ray diffractometry/reflectometry (EDXD/EDXR) study of the evolution of face-centered cubic (fcc) Pt layer growth on MgO(100) by pulsed laser deposition as a function of the process parameters such as deposition temperature and deposition duration has been carried out. The aim of this study is to define the best experimental conditions to obtain a controlled film deposition selective on the Pt growth direction (either [111] or [002]). The evolution of the Pt surface morphology as a function of the deposition temperature (T(dep)) from 300 to 700 degrees C has been studied with STM and ED techniques. Results show that the Pt surface, characterized at T(dep) = 300 degrees C by a 3D island morphology, evolves at higher temperatures to a morphology in which the original islands coexist with a distribution of orthogonal 2D stripes. The two features can be associated with the [111] and [002] Pt growth directions of the fcc phase, respectively. For T(dep) = 700 degrees C, the island morphology of the (111) face completely disappears, while the merging process of the (002) stripes reaches completion. The evolution of the morphology at T(dep) = 600 degrees C as a function of the deposition time and thickness has then been studied with STM-UHV, revealing an initial growth of mosaic-like 3D islands. These independent islands, already interconnected, expand along two orthogonal directions and, for longer deposition times, lead to the texture of orthogonal stripes. The EDXR characterization providing the morphological parameters of the films, i.e., thickness and roughness, confirms the above observation and quantifies the effect of such morphological changes on the surface roughness of the Pt film, an important parameter for applications of Pt films as underlayer in magnetic recording media.     

Predicting physical-chemical properties of compounds from molecular structures by recursive neural networks

In this paper, we report on the potential of a recently developed neural network for structures applied to the prediction of physical chemical properties of compounds. The proposed recursive neural network (RecNN) model is able to directly take as input a structured representation of the molecule and to model a direct and adaptive relationship between the molecular structure and target property. Therefore, it combines in a learning system the flexibility and general advantages of a neural network model with the representational power of a structured domain. As a result, a completely new approach to quantitative structure-activity relationship/quantitative structure-property relationship (QSPR/QSAR) analysis is obtained. An original representation of the molecular structures has been developed accounting for both the occurrence of specific atoms/groups and the topological relationships among them. Gibbs free energy of solvation in water, Delta(solv)G degrees , has been chosen as a benchmark for the model. The different approaches proposed in the literature for the prediction of this property have been reconsidered from a general perspective. The advantages of RecNN as a suitable tool for the automatization of fundamental parts of the QSPR/QSAR analysis have been highlighted. The RecNN model has been applied to the analysis of the Delta(solv)G degrees in water of 138 monofunctional acyclic organic compounds and tested on an external data set of 33 compounds. As a result of the statistical analysis, we obtained, for the predictive accuracy estimated on the test set, correlation coefficient R = 0.9985, standard deviation S = 0.68 kJ mol(-1), and mean absolute error MAE = 0.46 kJ mol(-1). The inherent ability of RecNN to abstract chemical knowledge through the adaptive learning process has been investigated by principal components analysis of the internal representations computed by the network. It has been found that the model recognizes the chemical compounds on the basis of a nontrivial combination of their chemical structure and target property.     

Sharp boundary behaviour of solutions to semilinear nonlocal elliptic equations

We investigate quantitative properties of nonnegative solutions \(u(x)\ge 0\) to the semilinear diffusion equation \(\mathcal {L}u= f(u)\), posed in a bounded domain \(\Omega \subset \mathbb {R}^N\) with appropriate homogeneous Dirichlet or outer boundary conditions. The operator \(\mathcal {L}\) may belong to a quite general class of linear operators that include the standard Laplacian, the two most common definitions of the fractional Laplacian \((-\Delta )^s\) (\(0<s<1\)) in a bounded domain with zero Dirichlet conditions, and a number of other nonlocal versions. The nonlinearity f is increasing and looks like a power function \(f(u)\sim u^p\), with \(p\le 1\). The aim of this paper is to show sharp quantitative boundary estimates based on a new iteration process. We also prove that, in the interior, solutions are Hölder continuous and even classical (when the operator allows for it). In addition, we get Hölder continuity up to the boundary. Particularly interesting is the behaviour of solution when the number \(\frac{2s}{1-p}\) goes below the exponent \(\gamma \in (0,1]\) corresponding to the Hölder regularity of the first eigenfunction \(\mathcal {L}\Phi _1=\lambda _1 \Phi _1\). Indeed a change of boundary regularity happens in the different regimes \(\frac{2s}{1-p} \gtreqqless \gamma \), and in particular a logarithmic correction appears in the “critical” case \(\frac{2s}{1-p} = \gamma \). For instance, in the case of the spectral fractional Laplacian, this surprising boundary behaviour appears in the range \(0<s\le (1-p)/2\).