Impact of the exchange-correlation functional on the structure of glassy GeSe2

The structural properties of glassy GeSe₂ were studied by using first-principles molecular dynamics with the Becke, Lee, Yang and Parr (BLYP) expression for the exchange-correlation energy within density functional theory. A comparison is made with the results previously obtained for this material by using first-principles molecular dynamics with the Perdew and Wang (PW) exchange-correlation functional. Overall, the structures of the BLYP-GeSe₂ and PW-GeSe₂ networks are quite similar, the BLYP approach favoring a larger number of Ge–Ge homopolar bonds, in better agreement with the experimental results. The BLYP network does, however, feature a smaller fraction of corner-sharing motifs by comparison with the PW network but the fraction of edge-sharing motifs is the same for both structures, at least within the confines of an approach based on a single temporal trajectory. Further studies are required to determine whether agreement between the BLYP structure and experiment can be improved by taking the average over a larger number of temporal trajectories or whether additional developments are required for the exchange-correlation part of the energy functional.     

Some Observations on Testing Conditions of High-Temperature Experiments on Concrete: An Insight from Neutron Tomography

Transport in Porous Media - This communication explores the influence of boundary effects, embedded sensors and crack opening on high-temperature experiments of concrete as revealed by in situ...     

Mapping C−H⋅⋅⋅M Interactions in Confined Spaces: (α-ICyDMe)Au,Ag, Cu Complexes Reveal “Contra-electrostatic H Bonds” Masquerading as Anagostic Interactions**

What happens when a C−H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as “contra-electrostatic” H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. While electrostatics is strongly stabilizing component in the conventional C−H⋅⋅⋅X bonds where X is an electronegative main group element, it is destabilizing in the C−H⋅⋅⋅M contacts when M is Au(I), Ag(I), or Cu(I) of NHC−M−Cl systems. Such remarkable C−H⋅⋅⋅M interaction became experimentally accessible within (α-ICyD^Me)MCl, NHC-Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C−H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of d-orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C−H bond to point toward the metal, and reveals a still attractive “contra-electrostatic” H-bonding interaction.     

Facile Conversion of Molecularly Complex (Hetero)aryl Carboxylic Acids into Alkynes for Accelerated SAR Exploration

1,2,3-Triazoles are well-established bioisosteres for amides, often installed as a result of structure−activity-relationship (SAR) exploration. A straightforward approach to assess the effect of the replacement of an amide by a triazole would start from the carboxylic acid and the amine used for the formation of a given amide and convert them into the corresponding alkyne and azide for cyclization by copper-catalyzed alkyne−azide cycloaddition (CuAAC). Herein, we report a functional-group-tolerant and operationally simple decarbonylative alkynylation that allows the conversion of complex (hetero)aryl carboxylic acids into alkynes. Furthermore, the utility of this method was demonstrated in the preparation of a triazolo analog of the commercial drug moclobemide. Lastly, mechanistic investigations using labeled carboxylic acid derivatives clearly show the decarbonylative nature of this transformation.     

An Alternate [2×2] Grid Constructed Around TiO4N2 Units

The formation of a tetranuclear self-assembled species constructed around a TiO₄N₂ motif is reported. This aggregate is generated from Ti(OⁱPr)₄, 2,2’-bipyrimidine (bpym) and a bis-biphenol strand (L²H₄) where two 2,2’-biphenol units are connected with a biphenyl spacer. The solid-state structure of the [Ti₄(L²)₄(bpym)₄] architecture reveals the formation of an unprecedented chiral alternate [2×2] grid. In addition to the structural characterization of the [Ti₄(L²)₄(bpym)₄] architecture, geometry optimisation on various possible isomeric tetrameric assemblies ([2×2] grid, alternate [2×2] grid, circular helicate or cyclic hemihelicate) is performed using DFT calculations. These results confirm the higher stability of the alternate [2×2] grid over the other possible tetranuclear isomers and allow examining the replacement of the bpym ligands by two novel diimine chelates within the tetranuclear assembly (2,2’-bipyridine=bipy and 2,2’-bipyrazine=bipyraz). From this initial theoretical investigation, the competition between these three nitrogen ligands in the course of the self-assembly process is next evaluated. Overall, this investigation shows that the exclusive formation of the alternate [2×2] grid is driven by CH⋅⋅⋅N interactions.     

Existence of local strong solutions to fluid–beam and fluid–rod interaction systems

We study an unsteady nonlinear fluid–structure interaction problem. We consider a Newtonian incompressible two-dimensional flow described by the Navier–Stokes equations set in an unknown domain depending on the displacement of a structure, which itself satisfies a linear wave equation or a linear beam equation. The fluid and the structure systems are coupled via interface conditions prescribing the continuity of the velocities at the fluid–structure interface and the action-reaction principle. Considering three different structure models, we prove existence of a unique local-in-time strong solution, for which there is no gap between the regularity of the initial data and the regularity of the solution enabling to obtain a blow up alternative. In the case of a damped beam this is an alternative proof (and a generalization to non zero initial displacement) of the result that can be found in [20]. In the case of the wave equation or a beam equation with inertia of rotation, this is, to our knowledge the first result of existence of strong solutions for which no viscosity is added. The key points consist in studying the coupled system without decoupling the fluid from the structure and to use the fluid dissipation to control, in appropriate function spaces, the structure velocity.