Unveiling oxygen vacancy impact on lizardite thermo and mechanical properties.

Here, we performed a systematic DFT study assisted by the workflow framework SimStack for the mechanical and thermodynamic properties of the clay mineral lizardite in pristine and six different types of O vacancies configurations. In most cases, the defect caused a structural phase transition in the lizardite from the trigonal (pristine) to the triclinic phase. The results show that oxygen vacancies in lizardite significantly reduce the lattice thermal conductivity, accompanied by an elastic moduli reduction and an anisotropy index increase. Through the P-V relation, an increase in compressibility was evidenced for vacancy configurations. Except for the vacancy with the same crystalline structure as pristine lizardite, the sound velocities of the other vacancy configurations produce a decrease in these velocities, and it is essential to highlight high values for the Grüneisen parameter. We emphasize the great relevance of the punctual-defects introduction, such as O vacancies, in lizardite, since this microstructural design is responsible for the decrease of the lattice thermal conductivity in comparison with the pristine system by decreasing the heat transfer ability, turning lizardite into a promising candidate for thermoelectric materials.

Perfluoropropionic Acid-Driven Nucleation of Atmospheric Molecules under Ambient Conditions.

A molecular-level understanding of the compositions and formation mechanism of secondary organic aerosols is important in the context of growing evidence regarding the adverse impacts of aerosols on the atmosphere and human health. The ever-growing emissions of pollutants and particulate matter in the atmosphere are a global concern. A particular class of pollutants, which are being important in this sense, are persistent organic pollutants (POPs) since they represent synthetic organic compounds with a long lifetime in the environment. Among the POPs, the perfluorinated compounds, such as perfluoroalkyl carboxylic acids (CnF2n+1COOH) or PFCAs, draw a lot of attention due to their adverse effect on human health. In the present work, we employ high-level density functional theory to investigate the electrostatic interaction of perfluoropropionic acid (C2F5COOH) or PFPA, a PFCA with n = 2, with well-known atmospheric molecules, namely, HCHO, HCOOH, CH3OH, H2SO4, and CH3SO3H [methanesulfonic acid (MSA)]. A detailed and systematic quantum chemical calculation has been performed to analyze the structural, energetic, electrical, and spectroscopic properties of several binary clusters in the context of atmospheric nucleation process. Our analysis shows that PFPA forms very stable hydrogen-bonded binary clusters with molecules like H2SO4 and MSA, which widely recognized atmospheric nucleation precursors. Scattering intensities of radiation (Rayleigh activities) are found to increase many fold when PFPA forms clusters. Analyses of the cluster-binding electronic energies and the free-energy changes associated with their formation at different temperatures indicate that PFPA could participate in the initial nucleation processes and contribute effectively to the new particle formation in the atmosphere.

PANI-WO3·2H2O Nanocomposite: Phase Interaction and Evaluation of Electronic Properties by Combined Experimental Techniques and Ab-Initio Calculation.

The development of conjugated polymer-based nanocomposites by adding metallic particles into the polymerization medium allows the proposition of novel materials presenting improved electrical and optical properties. Polyaniline Emeraldine-salt form (ES-PANI) has been extensively studied due to its controllable electrical conductivity and oxidation states. On the other hand, tungsten oxide (WO3) and its di-hydrated phases, such as WO3·2H2O, have been reported as important materials in photocatalysis and sensors. Herein, the WO3·2H2O phase was directly obtained during the in-situ polymerization of aniline hydrochloride from metallic tungsten (W), allowing the formation of hybrid nanocomposites based on its full oxidation into WO3·2H2O. The developed ES-PANI-WO3·2H2O nanocomposites were successfully characterized using experimental techniques combined with Density Functional Theory (DFT). The formation of WO3·2H2O was clearly verified after two hours of synthesis (PW2 nanocomposite), allowing the confirmation of purely physical interaction between matrix and reinforcement. As a result, increased electrical conductivity was verified in the PW2 nanocomposite: the DFT calculations revealed a charge transfer from the p-orbitals of the polymeric phase to the d-orbitals of the oxide phase, resulting in higher conductivity when compared to the pure ES-PANI.

Efficient coding and multiple motions.

Based on the principle of efficient coding, we present a theoretical framework for how to categorize the basic types of changes that can occur in a spatio-temporal signal. First, theoretical results for the problem of estimating multiple transparent motions are reviewed. Then, confidence measures for the presence of multiple motions are used to derive a basic alphabet of local signal variation that includes motion layers. To better understand and visualize this alphabet, a representation of motions in the projective plane is used. A further, practical contribution is an interactive tool that allows generating multiple motion patterns and displaying them in various apertures. In our framework, we can explain some well-known results on coherent motion and a few more complex perceptual phenomena such as the 2D-1D entrainment effect, but the focus of this paper is on the methods. Our working hypothesis is that efficient representations can be obtained by suppressing all the redundancies that arise if the visual input does not change in a particular direction, or a set of directions. Finally, we assume that human eye movements will tend to avoid the redundant parts of the visual input and report results where our framework has been used to obtain very good predictions of eye movements made on overlaid natural videos.

Analysis of superimposed oriented patterns.

Estimation of local orientation in images may be posed as the problem of finding the minimum gray-level variance axis in a local neighborhood. In bivariate images, the solution is given by the eigenvector corresponding to the smaller eigenvalue of a 2 x 2 tensor. For an ideal single orientation, the tensor is rank-deficient, i.e., the smaller eigenvalue vanishes. A large minimal eigenvalue signals the presence of more than one local orientation, what may be caused by non-opaque additive or opaque occluding objects, crossings, bifurcations, or corners. We describe a framework for estimating such superimposed orientations. Our analysis is based on the eigensystem analysis of suitably extended tensors for both additive and occluding superpositions. Unlike in the single-orientation case, the eigensystem analysis does not directly yield the orientations, rather, it provides so-called mixed-orientation parameters (MOPs). We, therefore, show how to decompose the MOPs into the individual orientations. We also show how to use tensor invariants to increase efficiency, and derive a new feature for describing local neighborhoods which is invariant to rigid transformations. Applications are, e.g., in texture analysis, directional filtering and interpolation, feature extraction for corners and crossings, tracking, and signal separation.