Energy decomposition analysis of metal-metal bonding in [M2X8]2- (X=Cl, br) complexes of 5f (U, Np, Pu), 5d (W, Re, Os), and 4d (Mo, Tc, Ru) elements

The electronic structures of a series of [M2X8]2- (X=Cl, Br) complexes involving 5f (U, Np, Pu), 5d (W, Re, Os), and 4d (Mo, Tc, Ru) elements have been calculated using density functional theory, and an energy decomposition approach has been used to carry out a detailed analysis of the metal-metal interactions. The energy decomposition analysis involves contributions from orbital interactions (mixing of occupied and unoccupied orbitals), electrostatic effects (Coulombic attraction and repulsion), and Pauli repulsion (associated with four-electron two-orbital interactions). As previously observed for Mo, W, and U M2X6 species, the general results suggest that the overall metal-metal interaction is considerably weaker or unfavorable in the actinide systems relative to the d-block analogues, as a consequence of a significantly more destabilizing contribution from the combined Pauli and electrostatic (prerelaxation) effects. Although the orbital-mixing (postrelaxation) contribution to the total bonding energy is predicted to be larger in the actinide complexes, this is not sufficiently strong to compensate for the comparatively greater destabilization originating from the Pauli-plus-electrostatic effects. A generally weak electrostatic contribution accounts for the large prerelaxation destabilization in the f-block systems, and ultimately for the weak or unfavorable nature of metal-metal bonding between the actinide elements. There is a greater variation in the energy decomposition results across the [M2Cl8]2- series for the actinide than for the d-block elements, both in the general behavior and in some particular properties.     

Tough and tunable adhesion of hydrogels: experiments and models

As polymer networks infiltrated with water, hydro-gels are major constituents of animal and plant bodies and have diverse engineering applications. While natural hydro-gels can robustly adhere to other biological materials, such as bonding of tendons and cartilage on bones and adhe-sive plaques of mussels, it is challenging to achieve such tough adhesions between synthetic hydrogels and engineer-ing materials. Recent experiments show that chemically anchoring long-chain polymer networks of tough synthetic hydrogels on solid surfaces create adhesions tougher than their natural counterparts, but the underlying mechanism has not been well understood. It is also challenging to tune sys-tematically the adhesion of hydrogels on solids. Here, we provide a quantitative understanding of the mechanism for tough adhesions of hydrogels on solid materials via a com-bination of experiments, theory, and numerical simulations. Using a coupled cohesive-zone and Mullins-effect model val-idated by experiments, we reveal the interplays of intrinsic work of adhesion, interfacial strength, and energy dissipation in bulk hydrogels in order to achieve tough adhesions. We fur-ther show that hydrogel adhesion can be systematically tuned by tailoring the hydrogel geometry and silanization time of solid substrates, corresponding to the control of energy dis-sipation zone and intrinsic work of adhesion, respectively. The current work further provides a theoretical foundation for rational design of future biocompatible and underwater adhesives.     

On the paucity of molecular actinide complexes with unsupported metal-metal bonds: a comparative investigation of the electronic structure and metal-metal bonding in U2X6 (X = Cl, F, OH, NH2, CH3) complexes and d-block analogues

Density functional calculations have been performed on M2X6 complexes (where M = U, W, and Mo and X = Cl, F, OH, NH2, and CH3) to investigate general aspects of their electronic structures and explore the similarities and differences in metal-metal bonding between f-block and d-block elements. A detailed analysis of the metal-metal interactions has been conducted using molecular orbital theory and energy decomposition methods. Multiple (sigma and pi) bonding is predicted for all species investigated, with predominant f-f and d-d metal orbital character, respectively, for U and W or Mo complexes. The energy decomposition analysis involves contributions from orbital interactions (mixing of occupied and unoccupied orbitals), electrostatic effects (Coulombic attraction and repulsion), and Pauli repulsion (associated with four-electron two-orbital interactions). The general results suggest that the overall metal-metal interaction is stronger in the Mo and W species, relative to the U analogues, as a consequence of a significantly less destabilizing contribution from the combined Pauli and electrostatic ("pre-relaxation") effects. Although the orbital-mixing ("post-relaxation") contribution to the total bonding energy is predicted to have a larger magnitude in the U complexes, this is not sufficiently strong to compensate for the comparatively greater destabilization that originates from the Pauli-plus-electrostatic effects. Of the pre-relaxation terms, the Pauli repulsion is comparable in analogous U and d-block compounds, contrary to the electrostatic term, which is (much) less favorable in the U systems than in the W and Mo systems. This generally weak electrostatic stabilization accounts for the large pre-relaxation destabilization in the U complexes and, ultimately, for the relative weakness of the U-U bonds. The origin of the small electrostatic term in the U compounds is traced primarily to MX(3) fragment overlap effects.     

Strategies for bass enhancement in Multiactuator Panels for Wave Field Synthesis

In this paper, an extension of the useful bandwidth in the low frequency band is applied to compensate the inherent poor bass response of Multiactuator Panels. These are a special type of flat panel loudspeakers that are commonly used to reproduce spatial audio under the Wave Field Synthesis system. The proposed algorithm combines two strategies: first, a dynamic electrical equalization, applied to additional exciters, which are carefully positioned to excite the lower frequency modes of the panel; second, a psycho-acoustical approach, taking profit of the behavior of human hearing based on the missing fundamental principle. For comparison purposes, the shelving and peak equalizations are also applied to the MAP prototypes developed in this paper. Objective and subjective results show that the combined approach results in an effective extension in the low frequency end of MAP with very low levels of distortion, outperforming conventional equalization methods, with better low frequency behavior, and hence better audio quality perception.     

Measurement of Cumulative Yield of the $${}^{{103}}$$ Ru Radionuclide for $${}^{{4}}$$ He-, $${}^{{3}}$$ He-, Proton- and Deuteron-Induced Reactions on ThO $${}_{{2}}$$ Targets

Physics of Atomic Nuclei - Modular nanotransporters (MNTs) are promising technology for nuclear medicine of the present time which is based on an engineered polypeptide platform. Emitters of Auger...     

Force driven separation of drops by deterministic lateral displacement

We investigate the separation of drops in force-driven deterministic lateral displacement (f-DLD), a promising high-throughput continuous separation method in microfluidics. We perform scaled-up macroscopic experiments in which drops settle through a square array of cylindrical obstacles. These experiments demonstrate the separation capabilities-and provide insight for the design-of f-DLD for drops of multiple sizes, including drops that are larger than the gaps between cylinders and exhibit substantial deformation as they move through the array. We show that for any orientation of the driving force relative to the array of obstacles, the trajectories of the drops follow selected locking directions in the lattice. We also found that a simple collision model accurately describes the average migration angles of the drops for the entire range of sizes investigated here, and for all forcing directions. In addition, we found a difference of approximately 20° between the critical angles at which the smallest and largest drops first move across a line of obstacles (column) in the array, a promising result in terms of potential size resolution of this method. Finally, we demonstrate that a single line of cylindrical obstacles rotated with respect to the driving force is capable of performing binary separations. The critical angles obtained in such single line experiments, moreover, agree with those obtained using the full array, thus validating the assumption in which the trajectory (and average migration angle) of the drops is calculated from individual obstacle-drop collisions.     

Emulsion Polymerization of Styrene Mediated by TEMPO at Low Temperature

NMRP is a controlled polymerization technique with the ability to produce polymers with a highly controlled microstructure. The properties of the thus obtained polymers make it desirable to scale this technique to an industrial level, but there are still some challenges to be faced, e.g., to develop emulsion NMRP at low temperatures (lower than about 100 °C) with inexpensive, commercially available nitroxides such as TEMPO. Here, the emulsion NMRP of styrene using TEMPO at temperatures lower than 100 °C is described. An optimal control of molecular weights and polydispersities and a fast polymerization rate are obtained.