Computational and Experimental Evaluation of Peroxide Oxidants for Amine-Peroxide Redox Polymerization

Amine–peroxide redox polymerization (APRP) is the prevalent method for producing radical-based polymers in the many industrial and medical applications where light or heat activation is impractical. We recently developed a detailed description of the APRP initiation process through a combined computational and experimental effort to show that APRP proceeds through SN2 attack by the amine on the peroxide, followed by the rate-determining homolysis of the resulting intermediate. Using this new mechanistic understanding, a variety of peroxides were computationally predicted to initiate APRP with fast kinetics. In particular, the rate of APRP initiation can be improved by radical and anion stabilization through increased π-electron conjugation or by increasing the electrophilicity of the peroxy bond through the addition of electron-withdrawing groups. On the other hand, the addition of electron-donating groups lowered the initiation rate. These design principles enabled the computational prediction of several new peroxides that exhibited improved initiation rates over the commonly used benzoyl peroxide. For example, the addition of nitro groups (NO₂) to the para positions of benzoyl peroxide resulted in a theoretical radical generation rate of 1.9 × 10⁻⁹ s⁻¹, which is ∼150 times faster than the 1.3 × 10⁻¹¹ s⁻¹ radical generation rate observed with unsubstituted benzoyl peroxide. These accelerated kinetics enabled the development of a redox-based direct-writing process that exploited the extremely rapid reactivity of an optimized redox pair with a custom inkjet printer, capable of printing custom shapes from polymerizing resins without heat or light. Furthermore, the application of more rapid APRP kinetics could enable the acceleration of existing industrial processes, make new industrial manufacturing methods possible, and improve APRP compatibility with biomedical applications through reduced initiator concentrations that still produce rapid polymerization rates

Rotating solenoidal perfect fluids of Petrov type D

We prove that aligned Petrov type D perfect fluids for which the vorticity vector is not orthogonal to the plane of repeated principal null directions and for which the magnetic part of the Weyl tensor with respect to the fluid velocity has vanishing divergence, are necessarily purely electric or locally rotationally symmetric. The LRS metrics are presented explicitly.Comment: 6 pages, no figure

New Tolerance Factor to Predict the Stability of Perovskite Oxides and Halides

Predicting the stability of the perovskite structure remains a longstanding challenge for the discovery of new functional materials for many applications including photovoltaics and electrocatalysts. We developed an accurate, physically interpretable, and one-dimensional tolerance factor, {\tau}, that correctly predicts 92% of compounds as perovskite or nonperovskite for an experimental dataset of 576 $ABX_3$ materials ($\textit{X} =$ $O^{2-}$, $F^-$, $Cl^-$, $Br^-$, $I^-$) using a novel data analytics approach based on SISSO (sure independence screening and sparsifying operator). {\tau} is shown to generalize outside the training set for 1,034 experimentally realized single and double perovskites (91% accuracy) and is applied to identify 23,314 new double perovskites ($A_2$$\textit{BB'}$$X_6$) ranked by their probability of being stable as perovskite. This work guides experimentalists and theorists towards which perovskites are most likely to be successfully synthesized and demonstrates an approach to descriptor identification that can be extended to arbitrary applications beyond perovskite stability predictions

Dimension in a Radiative Stellar Atmosphere

Dimensional scales are examined in an extended 3+1 Vaidya atmosphere surrounding a Schwarzschild source. At one scale, the Vaidya null fluid vanishes and the spacetime contains only a single spherical 2-surface. Both of these behaviors can be addressed by including higher dimensions in the spacetime metric.Comment: to appear in Gen. Rel. Gra

Superposition of Weyl solutions: The equilibrium forces

Solutions to the Einstein equation that represent the superposition of static isolated bodies with axially symmetry are presented. The equations nonlinearity yields singular structures (strut and membranes) to equilibrate the bodies. The force on the strut like singularities is computed for a variety of situations. The superposition of a ring and a particle is studied in some detailComment: 31 pages, 7 figures, psbox macro. Submitted to Classical and Quantum Gravit