Université de Pau et des Pays de l'Adour

Over the past 30 years, conservation of resources (COR) theory has become one of the most widely cited theories in organizational psychology and organizational behavior. COR theory has been adopted across the many areas of the stress spectrum, from burnout to traumatic stress. Further attesting to the theory's centrality, COR theory is largely the basis for the more work-specific leading theory of organizational stress, namely the job demands-resources model. One of the major advantages of COR theory is its ability to make a wide range of specific hypotheses that are much broader than those offered by theories that focus on a single central resource, such as control, or that speak about resources in general. In this article, we will revisit the principles and corollaries of COR theory that inform those more specific hypotheses and will review research in organizational behavior that has relied on the theory.

autophagic responses. Here, we critically discuss current methods of assessing autophagy and the information they can, or cannot, provide. Our ultimate goal is to encourage intellectual and technical innovation in the field.

The latest release of the Crystal program for solid‐state quantum‐mechanical ab initio simulations is presented. The program adopts atom‐centered Gaussian‐type functions as a basis set, which makes it possible to perform all‐electron as well as pseudopotential calculations. Systems of any periodicity can be treated at the same level of accuracy (from 0D molecules, clusters and nanocrystals, to 1D polymers, helices, nanorods, and nanotubes, to 2D monolayers and slab models for surfaces, to actual 3D bulk crystals), without any artificial repetition along nonperiodic directions for 0–2D systems. Density functional theory calculations can be performed with a variety of functionals belonging to several classes: local‐density (LDA), generalized‐gradient (GGA), meta‐GGA, global hybrid, range‐separated hybrid, and self‐consistent system‐specific hybrid. In particular, hybrid functionals can be used at a modest computational cost, comparable to that of pure LDA and GGA formulations, because of the efficient implementation of exact nonlocal Fock exchange. Both translational and point‐symmetry features are fully exploited at all steps of the calculation, thus drastically reducing the corresponding computational cost. The various properties computed encompass electronic structure (including magnetic spin‐polarized open‐shell systems, electron density analysis), geometry (including full or constrained optimization, transition‐state search), vibrational properties (frequencies, infrared and Raman intensities, phonon density of states), thermal properties (quasi‐harmonic approximation), linear and nonlinear optical properties (static and dynamic [hyper]polarizabilities), strain properties (elasticity, piezoelectricity, photoelasticity), electron transport properties (Boltzmann, transport across nanojunctions), as well as X‐ray and inelastic neutron spectra. The program is distributed in serial, parallel, and massively parallel versions. In this paper, the original developments that have been devised and implemented in the last 4 years (since the distribution of the previous public version, Crystal14 , occurred in December 2013) are described. This article is categorized under: Software > Quantum Chemistry Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Density Functional Theory

The methodology presented within this work is a result of years of interactions between many junior and senior X-ray Photoelectron Spectroscopy (XPS) users operating within the CasaXPS spectral processing and interpretation program framework. In particular, discussions arising from a series of workshops have been a significant source for developing the overall XPS data processing concept and are the motivation for creating this work. These workshops organized by the Institut des Matériaux Jean Rouxel (IMN), Nantes gather both experienced and novice users of XPS for a week of discourse in conceptual experiment design and the resulting data processing. However, the framework constructed and utilized within these workshops encouraged the dissemination of knowledge beyond XPS data analysis and emphasized the importance of a multi-disciplinary collaborative approach to surface analysis problem-solving. The material presented here embodies data treatment originating from data made available to the first CNRS Thematic Workshop presented at Roscoff 2013. The methodology described here has evolved over the subsequent workshops in 2016 and 2019 and currently represents the philosophy used in CasaXPS spectral data processing paradigm.

The capabilities of the C rystal14 program are presented, and the improvements made with respect to the previous C rystal09 version discussed. C rystal14 is an ab initio code that uses a Gaussian‐type basis set: both pseudopotential and all‐electron strategies are permitted; the latter is not much more expensive than the former up to the first‐second transition metal rows of the periodic table. A variety of density functionals is available, including as an extreme case Hartree–Fock; hybrids of various nature (global, range‐separated, double) can be used. In particular, a very efficient implementation of global hybrids, such as popular B3LYP and PBE0 prescriptions, allows for such calculations to be performed at relatively low computational cost. The program can treat on the same grounds zero‐dimensional (molecules), one‐dimensional (polymers), two‐dimensional (slabs), as well as three‐dimensional (3D; crystals) systems. No spurious 3D periodicity is required for low‐dimensional systems as happens when plane‐waves are used as a basis set. Symmetry is fully exploited at all steps of the calculation; this permits, for example, to investigate nanotubes of increasing radius at a nearly constant cost (better than linear scaling!) or to perform self‐consistent‐field (SCF) calculations on fullerenes as large as (10,10), with 6000 atoms, 84,000 atomic orbitals, and 20 SCF cycles, on a single core in one day. Three versions of the code exist, serial, parallel, and massive‐parallel. In the second one, the most relevant matrices are duplicated, whereas in the third one the matrices in reciprocal space are distributed for diagonalization. All the relevant vectors are now dynamically allocated and deallocated after use, making C rystal14 much more agile than the previous version, in which they were statically allocated. The program now fits more easily in low‐memory machines (as many supercomputers nowadays are). C rystal14 can be used on parallel machines up to a high number of cores (benchmarks up to 10,240 cores are documented) with good scalability, the main limitation remaining the diagonalization step. Many tensorial properties can be evaluated in a fully automated way by using a single input keyword: elastic, piezoelectric, photoelastic, dielectric, as well as first and second hyperpolarizabilies, electric field gradients, Born tensors and so forth. Many tools permit a complete analysis of the vibrational properties of crystalline compounds. The infrared and Raman intensities are now computed analytically and related spectra can be generated. Isotopic shifts are easily evaluated, frequencies of only a fragment of a large system computed and nuclear contribution to the dielectric tensor determined. New algorithms have been devised for the investigation of solid solutions and disordered systems. The topological analysis of the electron charge density, according to the Quantum Theory of Atoms in Molecules, is now incorporated in the code via the integrated merge of the Topond package. Electron correlation can be evaluated at the Möller–Plesset second‐order level (namely MP2) and a set of double‐hybrids are presently available via the integrated merge with the C ryscor program. © 2014 Wiley Periodicals, Inc.

In recent years, the use of essential oils (EOs) derived from aromatic plants as low-risk insecticides has increased considerably owing to their popularity with organic growers and environmentally conscious consumers. EOs are easily produced by steam distillation of plant material and contain many volatile, low-molecular-weight terpenes and phenolics. The major plant families from which EOs are extracted include Myrtaceae, Lauraceae, Lamiaceae, and Asteraceae. EOs have repellent, insecticidal, and growth-reducing effects on a variety of insects. They have been used effectively to control preharvest and postharvest phytophagous insects and as insect repellents for biting flies and for home and garden insects. The compounds exert their activities on insects through neurotoxic effects involving several mechanisms, notably through GABA, octopamine synapses, and the inhibition of acetylcholinesterase. With a few exceptions, their mammalian toxicity is low and environmental persistence is short. Registration has been the main bottleneck in putting new products on the market, but more EOs have been approved for use in the United States than elsewhere owing to reduced-risk processes for these materials.

Lithium-ion (Li-ion) batteries that rely on cationic redox reactions are the primary energy source for portable electronics. One pathway toward greater energy density is through the use of Li-rich layered oxides. The capacity of this class of materials (>270 milliampere hours per gram) has been shown to be nested in anionic redox reactions, which are thought to form peroxo-like species. However, the oxygen-oxygen (O-O) bonding pattern has not been observed in previous studies, nor has there been a satisfactory explanation for the irreversible changes that occur during first delithiation. By using Li2IrO3 as a model compound, we visualize the O-O dimers via transmission electron microscopy and neutron diffraction. Our findings establish the fundamental relation between the anionic redox process and the evolution of the O-O bonding in layered oxides.

Abstract The perfectly matched layer (PML) absorbing boundary condition has proven to be very efficient from a numerical point of view for the elastic wave equation to absorb both body waves with nongrazing incidence and surface waves. However, at grazing incidence the classical discrete PML method suffers from large spurious reflections that make it less efficient for instance in the case of very thin mesh slices, in the case of sources located close to the edge of the mesh, and/or in the case of receivers located at very large offset. We demonstrate how to improve the PML at grazing incidence for the differential seismic wave equation based on an unsplit convolution technique. The improved PML has a cost that is similar in terms of memory storage to that of the classical PML. We illustrate the efficiency of this improved convolutional PML based on numerical benchmarks using a finite-difference method on a thin mesh slice for an isotropic material and show that results are significantly improved compared with the classical PML technique. We also show that, as the classical PML, the convolutional technique is intrinsically unstable in the case of some anisotropic materials.

A database of 15,617 point measurements of dimethylsulfide (DMS) in surface waters along with lesser amounts of data for aqueous and particulate dimethylsulfoniopropionate concentration, chlorophyll concentration, sea surface salinity and temperature, and wind speed has been assembled. The database was processed to create a series of climatological annual and monthly 1°×1° latitude‐longitude squares of data. The results were compared to published fields of geophysical and biological parameters. No significant correlation was found between DMS and these parameters, and no simple algorithm could be found to create monthly fields of sea surface DMS concentration based on these parameters. Instead, an annual map of sea surface DMS was produced using an algorithm similar to that employed by Conkright et al. [1994]. In this approach, a first‐guess field of DMS sea surface concentration measurements is created and then a correction to this field is generated based on actual measurements. Monthly sea surface grids of DMS were obtained using a similar scheme, but the sparsity of DMS measurements made the method difficult to implement. A scheme was used which projected actual data into months of the year where no data were otherwise present.

Reversible anionic redox has rejuvenated the search for high-capacity lithium-ion battery cathodes. Real-world success necessitates the holistic mastering of this electrochemistry's kinetics, thermodynamics, and stability. Here we prove oxygen redox reactivity in the archetypical lithium- and manganese-rich layered cathodes through bulk-sensitive synchrotron-based spectroscopies, and elucidate their complete anionic/cationic charge-compensation mechanism. Furthermore, via various electroanalytical methods, we answer how the anionic/cationic interplay governs application-wise important issues-namely sluggish kinetics, large hysteresis, and voltage fade-that afflict these promising cathodes despite widespread industrial and academic efforts. We find that cationic redox is kinetically fast and without hysteresis unlike sluggish anions, which furthermore show different oxidation vs. reduction potentials. Additionally, more time spent with fully oxidized oxygen promotes voltage fade. These fundamental insights about anionic redox are indispensable for improving lithium-rich cathodes. Moreover, our methodology provides guidelines for assessing the merits of existing and future anionic redox-based high-energy cathodes, which are being discovered rapidly.

We report the results of a comprehensive study on the structural, electronic, and optical properties of ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ in its ambient, monoclinic $(\ensuremath{\beta})$ and high-pressure, hexagonal $(\ensuremath{\alpha})$ phases in the framework of all-electron density functional theory. In both phases, the conduction band minimum is at the zone center while the valance band maximum is rather flat in the $k$ space. The calculated electron effective mass ${m}_{e}^{*}∕{m}_{0}$ comes out to be 0.342 and 0.276 for $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ and $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$, respectively. The dynamic dielectric function, reflectance, and energy-loss function for both phases are reported for a wide energy range of $0--50\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$. The subtle differences in electronic and optical properties can be attributed to the higher symmetry, coordination number of Ga atoms, and packing density in $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ relative to that in $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$.

Li-S rechargeable batteries are attractive for electric transportation because of their low cost, environmentally friendliness, and superior energy density. However, the Li-S system has yet to conquer the marketplace, owing to its drawbacks, namely, soluble polysulfide formation. To tackle this issue, we present here a strategy based on the use of a mesoporous chromium trimesate metal-organic framework (MOF) named MIL-100(Cr) as host material for sulfur impregnation. Electrodes containing sulfur impregnated within the pores of the MOF were found to show a marked increase in the capacity retention of Li-S cathodes. Complementary transmission electron microscopy and X-ray photoelectron spectroscopy measurements demonstrated the reversible capture and release of the polysulfides by the pores of MOF during cycling and evidenced a weak binding between the polysulphides and the oxygenated framework. Such an approach was generalized to other mesoporous oxide structures, such as mesoporous silica, for instance SBA-15, having the same positive effect as the MOF on the capacity retention of Li-S cells. Besides pore sizes, the surface activity of the mesoporous additives, as observed for the MOF, appears to also have a pronounced effect on enhancing the cycle performance. Increased knowledge about the interface between polysulfide species and oxide surfaces could lead to novel approaches in the design and fabrication of long cycle life S electrodes.

Argyrodite Li6PS5Cl is a good candidate for being a solid electrolyte for bulk all-solid-state Li-ion batteries because of its high ionic conductivity and its good processability. However, the interface stability of sulfide-based electrolytes toward active materials (negative or positive electrodes) is known to be lower than that of oxide-based electrolytes. In this work, we investigate the interface stability of argyrodite toward several positive electrode materials: LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4. All-solid-state half-cells were cycled, and the interface mechanisms were characterized by Auger electron spectroscopy and X-ray photoelectron spectroscopy. We show that Li6PS5Cl is oxidized into elemental sulfur, lithium polysulfides, P2Sx (x ≥ 5), phosphates, and LiCl at the interface with the positive electrode active materials. In spite of this interface reactivity, good capacity retention was observed over 300 cycles. Li6PS5Cl shows some reversible electrochemical activity (redox processes) that might contribute to the reversible capacity of the battery.

Largely based on its very high rechargeable capacity, silicon appears as an ideal candidate for the next generation of negative electrodes for Li-ion batteries. However, a crucial problem with silicon is the large volume expansion undergone upon alloying with lithium, which results in stability problems. Means to avoid such problems are largely linked to the understanding of the interfacial chemistry during charging/discharging. This is especially of great importance when using nanometric silicon particles. In this work, the interfacial mechanisms (reaction of surface oxide, Li–Si alloying process, and passivation layer formation) accompanying lithium insertion/extraction into Si/C/CMC composite electrodes have been scrutinized by X-ray photoelectron spectroscopy (XPS). A thorough nondestructive depth-resolved analysis was carried out by using both soft X-rays (100–800 eV) and hard X-rays (2000–7000 eV) from two different synchrotron facilities compared with in-house XPS (1487 eV). The unique combination utilizing hard and soft X-ray photoelectron spectroscopy accompanied with variation of the analysis depth allowed us to access interfacial phase transitions at the surface of silicon particles as well as the composition and thickness of the SEI (electrode/electrolyte interface layer).

The different techniques and methods employed as well as the different quantitative and qualitative variables measured in order to objectify postural control are often chosen without taking into account the population studied, the objective of the postural test, and the environmental conditions. For these reasons, the aim of this review was to present and justify the different testing techniques and methods with their different quantitative and qualitative variables to make it possible to precisely evaluate each sensory, central, and motor component of the postural function according to the experiment protocol under consideration. The main practical and technological methods and techniques used in evaluating postural control were explained and justified according to the experimental protocol defined. The main postural conditions (postural stance, visual condition, balance condition, and test duration) were also analyzed. Moreover, the mechanistic exploration of the postural function often requires implementing disturbing postural conditions by using motor disturbance (mechanical disturbance), sensory stimulation (sensory manipulation), and/or cognitive disturbance (cognitive task associated with maintaining postural balance) protocols. Each type of disturbance was tackled in order to facilitate understanding of subtle postural control mechanisms and the means to explore them.

Lithium deintercalation of LixCoO2 from x = 1 to x ≈ 0 has been carried out electrochemically. The changes in the electronic structure from LiCoO2 to CoO2 have been investigated by X-ray photoelectron spectroscopy (XPS) to bring some new developments about the electron transfer mechanisms upon lithium deintercalation. All available XPS core peaks (Co 2p, Co 3p, Co 3s, O 1s, F 1s, P 2p, C 1s) and valence spectra have been analyzed. The contributions of the electrode material and of the electrode/electrolyte interface have been clearly distinguished. We show that cobalt and oxygen simultaneously undergo a partial oxidation process and that the sole participation of oxygen atoms to the charge transfer process, as it is sometimes assumed, can be excluded. The surface film consists of organic and inorganic species resulting from degradation of the electrolyte.

A comprehensive study is reported entailing optimization of sodium ion electrolyte formulation and compatibility studies with positive and negative electrode materials. EC:PC:DMC and EC:PC:DME were found to exhibit optimum ionic conductivities and lower viscosities. Yet, hard carbon negative electrode materials tested in such electrolytes exhibit significant differences in performance, rooted in the different resistivity of the SEI, which results in too large polarization and concomitant loss of capacity at low potentials when DME is used as a co-solvent. EC0.45:PC0.45:DMC0.1 was found to be the optimum composition resulting in good rate capability and high capacity upon sustained cycling for hard carbon electrodes. Its compatibility with positive Na3V2(PO4)2F3 (NVPF) electrodes was also confirmed, which led to the assembly of full Na-ion cells displaying an operation voltage of 3.65 V, very low polarisation and excellent capacity retention upon cycling with ca. 97 mA h g−1 of NVPF after more than 120 cycles together with satisfactory coulombic efficiency (>98.5%) and very good power performance. Such values lead to energy densities comparable to those of the current state-of-the-art lithium-ion technology.

Understanding the origin of the high capacity displayed by Li2MnO3–LiMO2 (M = Ni, Co) composites is essential for improving their cycling and rate capability performances. To address this issue, the Li2Ru1–yMnyO3 series between the iso-structural layered end-members Li2MnO3 and Li2RuO3 was investigated. A complete solid solution was found, with the 0.4 ≤ y ≤ 0.6 members showing sustainable reversible capacities exceeding 220 mAh·g–1 centered around 3.6 V vs Li+/Li. The voltage–composition profiles display a plateau on the first charge as compared to an S-type curve on subsequent discharge which is maintained on the following charges/discharges, with therefore a lowering of the average voltage. We show this profile to evolve upon long cycling due to a structural phase transition as deduced from XRD measurements. Finally we demonstrate, via XPS measurements, the oxidation and reduction of ruthenium (Ru5+/Ru4+) during cycling together with a partial activity of the Mn4+/Mn3+ redox couple. Moreover, we provide direct evidence for the reversibility of the O2– → O– anionic process upon cycling, hence accounting for the high capacity displayed by these materials. This work, by capturing the main redox processes pertaining to these materials, should facilitate their development.

Document de travail IDEI ; 75 (C13 IDEI 75) Diffusion du document : IDEI Manufacture des Tabacs 21 allées de Brienne 31000 Toulouse (FRA) <br/>75

Traffic analysis is a compound of strategies intended to find relationships, patterns, anomalies, and misconfigurations, among others things, in Internet traffic. In particular, traffic classification is a subgroup of strategies in this field that aims at identifying the application's name or type of Internet traffic. Nowadays, traffic classification has become a challenging task due to the rise of new technologies, such as traffic encryption and encapsulation, which decrease the performance of classical traffic classification strategies. Machine learning (ML) gains interest as a new direction in this field, showing signs of future success, such as knowledge extraction from encrypted traffic, and more accurate Quality of Service management. ML is fast becoming a key tool to build traffic classification solutions in real network traffic scenarios; in this sense, the purpose of this investigation is to explore the elements that allow this technique to work in the traffic classification field. Therefore, a systematic review is introduced based on the steps to achieve traffic classification by using ML techniques. The main aim is to understand and to identify the procedures followed by the existing works to achieve their goals. As a result, this survey paper finds a set of trends derived from the analysis performed on this domain; in this manner, the authors expect to outline future directions for ML-based traffic classification.