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Size-driven transition of an antiferroelectric into a polar ferroelectric or ferrielectric state is a strongly debated issue from both experimental and theoretical perspectives. While critical thickness limits for such transitions have been explored, a bottom-up approach in the ultrathin limit considering few atomic layers could provide insight into the mechanism of stabilization of the polar phases over the antipolar phase seen in bulk PbZrO3. Here, we use first-principles density functional theory to predict the stability of polar phases in Pt/PbZrO3/Pt nanocapacitors. In a few atomic layer thick slabs of PbZrO3 sandwiched between Pt electrodes, we find that the polar phase originating from the well established R3c phase of bulk PbZrO3 is energetically favorable over the antipolar phase originating from the Pbam phase of bulk PbZrO3. The famous triple-well potential of antiferroelectric PbZrO3 is modified in the nanocapacitor limit in such a way as to swap the positions of the global and local minima, stabilizing the polar phase relative to the antipolar one. The size effect is decomposed into the contributions from dimensionality reduction, surface charge screening, and interfacial relaxation, which reveals that it is the creation of well-compensated interfaces that stabilizes the polar phases over the antipolar ones in nanoscale PbZrO3. 

Abstract We report evidence of a finite density of states at the Fermi level at the surface of epitaxial thin films of the narrow bandgap Mott insulator Sr₃Ir₂O₇(001). The Brillouin zone critical points for Sr₃Ir₂O₇(001) thin films have been determined by a comparison of the band mapping from angle-resolved photoemission spectroscopy and low energy electron diffraction. Angle-resolved x-ray photoemission studies reveal the surface termination of Sr₃Ir₂O₇(001) is Sr–O. The absence of dispersion with photon energy, or changing wave vector along the surface normal, indicates the two-dimensional character of the bands contributing to the density of states close to the Fermi level for Sr₃Ir₂O₇(001) thin films. Thus, the finite density of states at the Fermi level is attributed to surface states or surface resonances. The appearance of a finite density of states at the Fermi level is consistent with the increased conductivity with decreasing film thickness for ultrathin Sr₃Ir₂O₇(001) films. 

Regulatory networks depict promoting or inhibiting interactions between molecules in a biochemical system. We introduce a category-theoretic formalism for regulatory networks, using signed graphs to model the networks and signed functors to describe occurrences of one network in another, especially occurrences of network motifs. With this foundation, we establish functorial mappings between regulatory networks and other mathematical models in biochemistry. We construct a functor from reaction networks, modeled as Petri nets with signed links, to regulatory networks, enabling us to precisely define when a reaction network could be a physical mechanism underlying a regulatory network. Turning to quantitative models, we associate a regulatory network with a Lotka-Volterra system of differential equations, defining a functor from the category of signed graphs to a category of parameterized dynamical systems. We extend this result from closed to open systems, demonstrating that Lotka-Volterra dynamics respects not only inclusions and collapsings of regulatory networks, but also the process of building up complex regulatory networks by gluing together simpler pieces. Formally, we use the theory of structured cospans to produce a lax double functor from the double category of open signed graphs to that of open parameterized dynamical systems. Throughout the paper, we ground the categorical formalism in examples inspired by systems biology. 

Incorporation of secondary redox-inactive cations into heterobimetallic complexes is an attractive strategy for modulation of metal-centered redox chemistry, but quantification of the consequences of incorporating strongly Lewis acidic trivalent cations has received little attention. Here, a family of seven heterobimetallic complexes that pair a redox-active nickel center with La3+, Y3+, Lu3+, Sr2+, Ca2+, K+, and Na+ (in the form of their triflate salts) have been prepared on a heteroditopic ligand platform to understand how chemical behavior varies across the comprehensive series. Structural data from X-ray diffraction analysis demonstrate that the positions adopted by the secondary cations in the crown-ether-like site of the ligand relative to nickel are dependent primarily on the secondary cations’ ionic radii and that the triflate counteranions are bound to the cations in all cases. Electrochemical data, in concert with electron paramagnetic resonance studies, show that nickel(II)/nickel(I) redox is modulated by the secondary metals; the heterogeneous electron-transfer rate is diminished for the derivatives incorporating trivalent metals, an effect that is dependent on steric crowding about the nickel metal center and that was quantified here with a topographical free-volume analysis. As related analyses carried out here on previously reported systems bear out similar relationships, we conclude that the placement and identity of both the secondary metal cations and their associated counteranions can afford unique changes in the (electro)chemical behavior of heterobimetallic species. 

We present an optical photometric and spectroscopic analysis of the fast-declining hydrogen-rich Type II supernova (SN) 2019nyk. The light curve properties of SN 2019nyk align well with those of other fast-declining Type II SNe, such as SNe 2013by and 2014G. SN 2019nyk exhibits a peak absolute magnitude of −18.09 ± 0.17 mag in theVband, followed by a rapid decline at 2.84  ±  0.03 mag (100 d)⁻¹during the recombination phase. The early spectra of SN 2019nyk exhibit high-ionisation emission features as well as narrow H Balmer lines, persisting until 4.1 d since explosion, indicating the presence of circumstellar material (CSM) in close proximity. A comparison of these features with other Type II SNe displaying an early interaction reveals similarities between these features and those observed in SNe 2014G and 2023ixf. We also compared the early spectra to literature models, estimating a mass-loss rate of the order of 10⁻³M_⊙yr⁻¹. Radiation hydrodynamical modelling of the light curve also suggests the mass loss from the progenitor within a short period prior to explosion, totalling 0.16M_⊙of material within 2900R_⊙of the progenitor. Furthermore, light curve modelling infers a zero-age main sequence mass of 15M_⊙for the progenitor, a progenitor radius of 1031R_⊙, and an explosion energy of 1.1 × 10⁵¹erg.