Chalcogen···Chalcogen Bonding in Molybdenum Disulfide, Molybdenum Diselenide and Molybdenum Ditelluride Dimers as Prototypes for a Basic Understanding of the Local Interfacial Chemical Bonding Environment in 2D Layered Transition Metal Dichalcogenides

An attempt was made, using computational methods, to understand whether the intermolecular interactions in the dimers of molybdenum dichalcogenides MoCh2 (Ch = chalcogen, element of group 16, especially S, Se and Te) and similar mixed-chalcogenide derivatives resemble the room temperature experimentally observed interactions in the interfacial regions of molybdenites and their other mixed-chalcogen derivatives. To this end, MP2(Full)/def2-TVZPPD level electronic structure calculations on nine dimer systems, including (MoCh2)2 and (MoChCh′2)2 (Ch, Ch′ = S, Se and Te), were carried out not only to demonstrate the energetic stability of these systems in the gas phase, but also to reproduce the intermolecular geometrical properties that resemble the interfacial geometries of 2D layered MoCh2 systems reported in the crystalline phase. Among the six DFT functionals (single and double hybrids) benchmarked against MP2(full), it was found that the double hybrid functional B2PLYPD3 has some ability to reproduce the intermolecular geometries and binding energies. The intermolecular geometries and binding energies of all nine dimers are discussed, together with the charge density topological aspects of the chemical bonding interactions that emerge from the application of the quantum theory of atoms in molecules (QTAIM), the isosurface topology of the reduced density gradient noncovalent index, interaction region indicator and independent gradient model (IGM) approaches. While the electrostatic surface potential model fails to explain the origin of the S···S interaction in the (MoS2)2 dimer, we show that the intermolecular bonding interactions in all nine dimers examined are a result of hyperconjugative charge transfer delocalizations between the lone-pair on (Ch/Ch′) and/or the π-orbitals of a Mo–Ch/Ch′ bond of one monomer and the dπ* anti-bonding orbitals of the same Mo–Ch/Ch′ bond in the second monomer during dimer formation, and vice versa. The HOMO–LUMO gaps calculated with the MN12-L functional were 0.9, 1.0, and 1.1 eV for MoTe2, MoSe2 and MoS2, respectively, which match very well with the solid-state theoretical (SCAN-rVV10)/experimental band gaps of 0.75/0.88, 0.90/1.09 and 0.93/1.23 eV of the corresponding systems, respectively. We observed that the gas phase dimers examined are perhaps prototypical for a basic understanding of the interfacial/inter-layer interactions in molybdenum-based dichalcogenides and their derivatives.

A study on the isolated photon production in nuclear collisions at the CERN-LHC energies

An analysis of prompt photon production in high energy nuclear collisions at the LHC is performed within the parton saturation picture taking into account the updated phenomenological color dipole models. Comparison between $\langle N_{coll}\rangle$ scaling for hard scattering in heavy-ion collisions and the $N_{part}$-scaling based on geometric scaling arguments has been done. The predictions are parameter free in the first case whereas a dependence on the constant of proportionality $\kappa$ between the number of participants and the nuclear saturation scale appears in the second case. This parameter has been analyzed in the prompt photon spectrum at small transverse momentum even though no fitting procedure was performed. Results are confronted with the measurements made by the ALICE, ATLAS, and CMS experiments in terms of photon transverse momentum at different rapidity bins. We show that the prompt photon production exhibits distinct scalings in $AA$ events associated to geometrical properties of the collision and can be properly addressed in the color dipole formalism. Based on the $N_{part}$-scaling, an analytical parametrization for the invariant cross section is provided and employed to predict the $x_T$-scaling in measurements. For $\kappa$ of order of unit the theoretical scaling curve correctly describes data in the range $x_T\leq 5\times 10^{-2}$.

Experimental study of composite concrete cellular steel beams

The main objective of this study is to compare the structural behavior of composite steel– concrete beams using cellular beams with and without steel ring stiffeners placed around the web openings. An IPE140 hot rolled I-section steel beam was used to create four specimens: one without openings (control beam); one without shear connectors (non-composite); a composite steel–concrete beam using a cellular beam without strengthening (CLB1); and a composite steel–concrete beam using a cellular beam (CLB4-R) with its openings strengthened by steel ring stiffeners with geometrical properties Br = 37mm and Tr = 5mm. CLB1 was fabricated with openings of 100mm diameter and a 1.23 expansion depth ratio, while CLB4-R was fabricated with openings of 130mm diameter, a 1.42 expansion depth ratio. Both beams were 1700mm in length with ten openings. The results of this experiment revealed that the loads applied to CLB1 and CLB4-R at deflection L/360 exceeded the load applied to the control specimen at the same deflection by 149.3% and 177.3%, respectively. The results revealed that the non-composite beam had an ultimate load 29% lower than that of the control beam. The ultimate load on CLB1 was 5.3% greater than that of the control beam, and failure occurred due to web-post buckling. While the ultimate load of the CLB4-R beam was 18.43% greater than that of the control beam, the Vierendeel mechanism was indicated as the failure mode.

Drop of Pressure Behavior of Open-Cell Aluminum Foams at High Pressure Flow

Open-cell aluminum foams were produced by the replication technique in three different pore sizes, ranging from 0.71 to 4.75 mm. The manufactured specimens were physically characterized, determining their porosity, relative density, pores per inch and interconnection windows density. A new experimental design is proposed in order to assess the drop of pressure behavior resulting from the injection of gasoline additive at increasing high pressure intervals, ranging from 200 to 25,000 psi, reproducing the tests at room temperature and 200 °C. The regime governing the flow through the investigated samples was determined as a function of flowrate and the foams physical properties. The structural capacity of open-cell Al foams to conduct highly pressurized flow was evaluated by means of compression tests. It was found that at room temperature, the drop of pressure behavior is strongly associated to physical parameters, whilst at 200 °C, dimensional and geometrical properties are negligible. In addition, in this investigation, it is presumed that the studied foams have the structural capacity to conduct fluids at critical conditions of pressure and temperature.

Flutter Analysis of a 3D Box-Wing Aircraft Configuration

The aim of this paper is to present a flutter analysis of a 3D Box-Wing Aircraft (BWA) configuration. The box wing structure is considered as consisting of two wings (front and rear wings) connected with a winglet. Plunge and pitch motions are considered for each wing and the winglet is modeled by a longitudinal spring. In order to exert the effect of the wing-joint interactions (bending and torsion coupling), two ends of the spring are located on the gravity centers of the wings tip sections. Wagner unsteady model is used to simulate the aerodynamic force and moment on the wing. The governing equations are extracted via Hamilton’s variational principle. To transform the resulting partial integro-differential governing equations into a set of ordinary differential equations, the assumed modes method is utilized. In order to confirm the aerodynamic model, the flutter results of a clean wing are compared and validated with the previously published results. Also, for the validation, the 3D box wing aircraft configuration flutter results are compared with MSC NASTRAN software and good agreement is observed. The effects of design parameters such as the winglet tension stiffness, the wing sweep and dihedral angles, and the aircraft altitude on the flutter velocity and frequency are investigated. The results reveal that physical and geometrical properties of the front and rear wings and also the winglet design have a significant influence on BWA aeroelastic stability boundary.

Reliability Quantification of Railway Electrification Mast Structure Considering Buckling

This paper aims to quantify and assess the reliability of mast structures as a part of ensuring structure safety. The mast structure is a basic aspect of the overhead line electrification equipment (OHLE) used in railway systems. This structure is very important as the failure of structure leads to the failure of an electric system that supplies the power to the train. To ensure structural safety and reliability, this paper thus analyses the reliability index of the mast, stay tube, and bracket tube structures. According to Eurocode, buckling resistance under compression of these parts were calculated based on specific material properties, and the load condition of these structures is based on Australian Railcorp document TMC331. In this paper, the strength load combination with the wind loading on the wire at 45° on the track is considered in particular as being the worst load combination for structures to bear, and the random variables used to affect reliability probabilistic analysis. Various parameters including self-weight, wind load, dimension parameters, materials, geometrical properties are taken into consideration. Statistical models of these parameters are taken from previous studies. The reliability index value was calculated via quantification of structure reliability using the first-order reliability method (FORM). Finally, a sensitivity analysis is used to evaluate the impacts of yield strength, length, cross-section, density, and load combination on reliability. The obtained results show that increasing length of structure can potentially reduce the reliability of mast structure to buckling resistance while the density of material also plays a major role in the reliability index. The findings will provide the structural safety criteria of the railway mast structure and improve the standard design to mitigate the risks and unplanned maintenance due to the uncertainties.

Mafic explosive volcanism at Llaima Volcano: 3D x-ray microtomography reconstruction of pyroclasts to constrain shallow conduit processes

Mafic volcanic activity is dominated by effusive to mildly explosive eruptions. Plinian and ignimbrite-forming mafic eruptions, while rare, are also possible; however, the conditions that promote such explosivity are still being explored. Eruption style is determined by the ability of gas to escape as magma ascends, which tends to be easier in low-viscosity, mafic magmas. If magma permeability is sufficiently high to reduce bubble overpressure during ascent, volatiles may escape from the magma, inhibiting violent explosive activity. In contrast, if the permeability is sufficiently low to retain the gas phase within the magma during ascent, bubble overpressure may drive magma fragmentation. Rapid ascent may induce disequilibrium crystallization, increasing viscosity and affecting the bubble network with consequences for permeability, and hence, explosivity. To explore the conditions that promote strongly explosive mafic volcanism, we combine microlite textural analyses with synchrotron x-ray computed microtomography of 10 pyroclasts from the 12.6 ka mafic Curacautín Ignimbrite (Llaima Volcano, Chile). We quantify microlite crystal size distributions (CSD), microlite number densities, porosity, bubble interconnectivity, bubble number density, and geometrical properties of the porous media to investigate the role of magma degassing processes at mafic explosive eruptions. We use an analytical technique to estimate permeability and tortuosity by combing the Kozeny-Carman relationship, tortuosity factor, and pyroclast vesicle textures. The groundmass of our samples is composed of up to 44% plagioclase microlites, > 85% of which are < 10 µm in length. In addition, we identify two populations of vesicles in our samples: (1) a convoluted interconnected vesicle network produced by extensive coalescence of smaller vesicles (> 99% of pore volume), and (2) a population of very small and completely isolated vesicles (< 1% of porosity). Computed permeability ranges from 3.0 × 10−13 to 6.3 × 10−12 m2, which are lower than the similarly explosive mafic eruptions of Tarawera (1886; New Zealand) and Etna (112 BC; Italy). The combination of our CSDs, microlite number densities, and 3D vesicle textures evidence rapid ascent that induced high disequilibrium conditions, promoting rapid syn-eruptive crystallization of microlites within the shallow conduit. We interpret that microlite crystallization increased viscosity while simultaneously forcing bubbles to deform as they grew together, resulting in the permeable by highly tortuous network of vesicles. Using the bubble number densities for the isolated vesicles (0.1-3−3 × 104 bubbles per mm3), we obtain a minimum average decompression rate of 1.4 MPa/s. Despite the textural evidence that the Curacautín magma reached the percolation threshold, we propose that rapid ascent suppressed outgassing and increased bubble overpressures, leading to explosive fragmentation. Further, using the porosity and permeability of our samples, we estimated that a bubble overpressure > 5 MPa could have been sufficient to fragment the Curacautín magma. Other mafic explosive eruptions report similar disequilibrium conditions induced by rapid ascent rate, implying that syn-eruptive disequilibrium conditions may control the explosivity of mafic eruptions more generally.

On Convex Functions Associated with Symmetric Cardioid Domain

The geometry of the image domain plays an important role in the characterization of analytic functions. Therefore, for a comprehensive and detailed study of these functions, a thorough analysis of the geometrical properties of their domains is of prime interest. In this regard, new geometrical structures are introduced and studied as an image domain and then their subsequent analytic functions are defined. Inspired and motivated by ongoing research, Malik et al. introduced a very innovative domain named the cardioid domain, which is symmetric about a real axis. Extending the same work on this symmetric cardioid domain, in this article, we provide a deeper analysis and define and study the convex functions associated with the symmetric cardioid domain, named cardio-convex functions.

Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design

In the search for new nonlinear optical (NLO) switching devices, expanded porphyrins have emerged as ideal candidates thanks to their tunable chemical and photophysical properties. Introducing meso-substituents to these macrocycles is a successful strategy to enhance the NLO contrasts. Despite its potential, the influence of meso-substitution on their structural and geometrical properties has been scarcely investigated. In this work, we pursue to grasp the underlying pivotal concepts for the fine-tuning of the NLO contrasts of hexaphyrin-based molecular switches, with a particular focus on the first hyperpolarizability related to the hyper-Rayleigh scattering (βHRS). Building further on these concepts, we also aim to develop a rational design protocol. Starting from the (un)substituted hexaphyrins with various π-conjugation topologies and redox states, structure-property relationships are established linking aromaticity, photophysical properties and βHRS responses. Ultimately, inverse molecular design using the best-first search algorithm is applied on the most favorable switches with the aim to further explore the combinatorial chemical compound space of meso-substituted hexaphyrins in search of high-contrast NLO switches. Two definitions of the figure-of-merit of the switch performance were used as target objectives in the optimization problem. Several meso-substitution patterns and their underlying characteristics are identified, uncovering molecular symmetry and the electronic nature of the substituents as the key players for fine-tuning the βHRS values and NLO contrasts of hexaphyrin-based switches.