Structural,electronic and mechanical properties of alkaline earth metal oxides MO (M=Be,Mg, Ca,Sr, Ba)

The structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba) in the cubic (B1, B2 and B3) phases and in the wurtzite (B4) phase are investigated using density functional theory calculations as implemented in VASP code. The lattice constants, cohesive energy, bulk modulus, band structures and the density of states are computed. The calculated lattice parameters are in good agreement with the experimental and the other available theoretical results. Electronic structure reveals that all the five alkaline earth metal oxides exhibit semiconducting behavior at zero pressure. The estimated band gaps for the stable wurtzite phase of BeO is 7.2 eV and for the stable cubic NaCl phases of MgO, CaO, SrO and BaO are 4.436 eV, 4.166 eV, 4.013 eV, and 2.274 eV respectively. A pressure induced structural phase transition occurs from wurtzite (B4) to NaCl (B1) phase in BeO at 112.1 GPa and from NaCl (B1) to CsCl (B2) phase in MgO at 514.9 GPa, in CaO at 61.3 GPa, in SrO at 42 GPa and in BaO at 14.5 GPa. The elastic constants are computed at zero and elevated pressures for the B4 and B1 phases for BeO and for the B1 and B2 phases in the case of the other oxides in order to investigate their mechanical stability, anisotropy and hardness. The sound velocities and the Debye temperatures are calculated for all the oxides using the computed elastic constants.     

Detection of a P-induced liquid ⇌ solid-phase transformation using multiple acoustic transducers in a multi-anvil apparatus

A technique for detecting and measuring phase transitions in a multi-anvil apparatus by measuring the change in travel time for a longitudinal sound wave as a function of pressure is reported. The system measures the time for pulsed ultrasonic signals to travel through a high pressure assembly with a sample in the center. Upon phase change from liquid to solid, the travel time shows an abrupt decrease due to the intrinsic increase in velocity in the sample and a reduced delay between the triggering of an amplitude threshold and the arrival of the waveform. As a proof of concept, results are shown for mercury as it undergoes pressure-induced liquid ? solid transitions at room temperature. We propose that this non-destructive technique may be valuable in situations where other in situ probing techniques cannot be readily used to provide information about changes of state and potentially to study transition kinetics at high pressures as well.     

Topological phase transitions and Thouless pumping of light in photonic waveguide arrays

Photonic waveguide arrays provide an excellent platform for simulating conventional topological systems, and they can also be employed for the study of novel topological phases in photonics systems. However, a direct measurement of bulk topological invariants remains a great challenge. Here we study topological features of generalized commensurate Aubry‐André‐Harper (AAH) photonic waveguide arrays and construct a topological phase diagram by calculating all bulk Chern numbers, and then explore the bulk‐edge correspondence by analyzing the topological edge states and their winding numbers. In contrast to incommensurate AAH models, diagonal and off‐diagonal commensurate AAH models are not topologically equivalent. In particular, there appear nontrivial topological phases with large Chern numbers and topological phase transitions. By implementing Thouless pumping of light in photonic waveguide arrays, we propose a simple scheme to measure the bulk Chern numbers.

     

Hydrodynamic stability of evaporation fronts in porous media

The stability of phase transition fronts in water flows through porous media is considered. In the short-wave approximation a linear stability analysis is carried out and a sufficient condition of hydrodynamic instability of the phase discontinuity is proposed. The problem of injection of a water-vapor mixture into a two-dimensional mixture-saturated formation is solved and its numerical solution is compared with an exact solution of the corresponding one-dimensional self-similar problem. It is discovered that, instead of the unstable discontinuities in the one-dimensional formulation, in the two-dimensional case a lengthy mixing zone with a characteristic scale that increases self-similarly with time is formed.     

An Optimal Control Problem for a Singular System of Solid–Liquid Phase Transition

In this article, we deal with a control problem for a singular system regarding a phase-field model which describes a solid–liquid transition by the Ginzburg–Landau theory. The purpose is to control the system by the means of the heat supply r able to guide it into a certain state with a solid (or liquid) part in a prescribed subset Ω₀ of the space domain Ω, and maintain it in this state during a period of time. The transition is described by a nonlinear differential system of two equations for the phase field and temperature. The control problem is set for some expressions of the cost functional which might reveal cases of physical interest. An approximating control problem is introduced and the existence of at least an optimal pair is proved. The first-order optimality conditions for the approximating problem are determined and a convergence result is given.     

SANS from Pluronic P85 in d-water

Small-angle neutron scattering (SANS) has been used to investigate Pluronic P85 (EO₂₆PO₄₀EO₂₆) copolymer in deuterated water. A range of P85 fractions were measured for a wide sample temperature window. A rich phase behavior is reported. Unimers were observed below the critical micelle formation condition. At fixed P85 fraction, a number of micellar phases were observed upon increasing temperature; first spherical micelles, then cylindrical micelles, then lamellar micelles. At the highest temperature, a demixed lamellae phase was observed. Analysis of the SANS data consisted in fits to an empirical Guinier-Porod model that was appropriate for data fitting in the various phases at low P85 fractions. When the P85 fraction increased, an inter-particle structure factor was included to analyze SANS data from concentrated spherical micelles. At high P85 fractions, paracrystalline structures were observed as evidenced by an enhanced inter-particle interaction peak. A phase diagram for P85/d-water was obtained showing the various phases. Focusing on the spherical micelles phase for one sample composition, a core-shell model was used to fit SANS data and obtain sizes and scattering length densities. Using material balance equations, information such as the aggregation number (i.e., number of Pluronic macromolecules per micelle) and the number of hydration water molecules in the shell region are determined.     

The Versatile Coordination Modes of Monophosphine‐o‐Carborane in the Formation of Iridium and Rhodium Complexes: Synthesis,Reactivity, and Characterization

Monophosphine‐o‐carborane has four competitive coordination modes when it coordinates to metal centers. To explore the structural transitions driven by these competitive coordination modes, a series of monophosphine‐o‐carborane Ir,Rh complexes were synthesized and characterized. [Cp*M(Cl)₂{1‐(PPh₂)‐1,2‐C₂B₁₀H₁₁}] (M=Ir ( 1 a ), Rh ( 1 b ); Cp*=η⁵‐C₅Me₅), [Cp*Ir(H){7‐(PPh₂)‐7,8‐C₂B₉H₁₁}] ( 2 a ), and [1‐(PPh₂)‐3‐(η⁵‐Cp*)‐3,1,2‐MC₂B₉H₁₀] (M=Ir ( 3 a ), Rh ( 3 b )) can be all prepared directly by the reaction of 1‐(PPh₂)‐1,2‐C₂B₁₀H₁₁ with dimeric complexes [(Cp*MCl₂)₂] (M=Ir, Rh) under different conditions. Compound 3 b was treated with AgOTf (OTf=CF₃SO₃^?) to afford the tetranuclear metallacarborane [Ag₂(thf)₂(OTf)₂{1‐(PPh₂)‐3‐(η⁵‐Cp*)‐3,1,2‐RhC₂B₉H₁₀}₂] ( 4 b ). The arylphosphine group in 3 a and 3 b was functionalized by elemental sulfur (1 equiv) in the presence of Et₃N to afford [1‐{(S)PPh₂}‐3‐(η⁵‐Cp*)‐3,1,2‐MC₂B₉H₁₀] (M=Ir ( 5 a ), Rh ( 5 b )). Additionally, the 1‐(PPh₂)‐1,2‐C₂B₁₀H₁₁ ligand was functionalized by elemental sulfur (2 equiv) and then treated with [(Cp*IrCl₂)₂], thus resulting in two 16‐electron complexes [Cp*Ir(7‐{(S)PPh₂}‐8‐S‐7,8‐C₂B₉H₉)] ( 6 a ) and [Cp*Ir(7‐{(S)PPh₂}‐8‐S‐9‐OCH₃‐7,8‐C₂B₉H₉)] ( 7 a ). Compound 6 a further reacted with nBuPPh₂, thereby leading to 18‐electron complex [Cp*Ir(nBuPPh₂)(7‐{(S)PPh₂}‐8‐S‐7,8‐C₂B₉H₁₀)] ( 8 a ). The influences of other factors on structural transitions or the formation of targeted compounds, including reaction temperature and solvent, were also explored.