Iodinated aluminum(III) corroles with long-lived triplet excited states

The first reported iodination of a corrole leads to selective functionalization of the four C-H bonds on one pole of the macrocycle. An aluminum(III) complex of the tetraiodinated corrole, which exhibits red fluorescence, possesses a long-lived triplet excited state.     

Applying structured scenario fusion to address multifaceted strategic challenges

This paper proposes an applied method by which to fuse multiple independently developed scenarios to serve as a basis for strategic studies in the national security operations research community. First, it describes the need to fuse scenarios methodically as a consequence of the evolution of global security conditions and as a matter of logic that might be otherwise overlooked. Second, it proposes applying Structured Scenario Fusion (SSF), a method that uses three stylized tables to systematically and transparently record the process of scenario fusion. Third, it provides an example application set in a hypothetical study of future security conditions in Somalia. It concludes that SSF offers a promising way to improve the pedigree, realism, and logic of assumptions underpinning scenario-based strategic studies, as well as the quality of strategic decisions and plans thereby justified.     

The role of diphenyl iodonium salt (DPI) in three‐component photoinitiator systems containing methylene blue (MB) and an electron donor

Three‐component initiators generally include a light‐absorbing photosensitizer, an electron donor that is often an amine, and the third component, which is usually an iodonium salt. To characterize the role of diphenyl iodonium chloride (DPI) in three‐component photoinitiator systems containing methylene blue (MB) as the photosensitizer, a systematic series of electron donors was used. The Rhem–Weller equation was used to verify the thermodynamic feasibility for photo‐induced electron transfer from the electron donors to the MB. Comparison of the photopolymerization rates of each two‐component initiator system (containing the photosensitizer and amine) to those of the corresponding three‐component system (with the addition of (DPI) allowed fundamental information regarding the role of the DPI to be obtained. It was concluded that the DPI enhances the photopolymerization kinetics in two ways: (1) it consumes an inactive MB neutral radical and produces an active phenyl radical, thereby regenerating the original methylene blue, and (2) it reduces the recombination reaction of the MB neutral radical and amine radical/cation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5863–5871, 2004     

Measurement of the dissolved oxygen concentration in acrylate monomers with a novel photochemical method

Because of the well‐known radical‐scavenging behavior, molecular oxygen is capable of inhibiting free‐radical chain polymerizations of unsaturated monomers. The deleterious effects of diffused oxygen in a polymerization system result in both a reduced polymerization rate and the loss of surface properties of a polymer film or coating. However, reliable data for oxygen concentration in organic monomers are relatively scarce because of the experimental and instrumental limitations of the commercially available techniques. In this study, a photochemical method was developed and was used to obtain the dissolved oxygen concentration in seven acrylate monomers. The principle of the method was to convert ground‐state molecular oxygen dissolved in monomer to the excited, singlet‐state oxygen and then react the singlet oxygen with a third compound (singlet oxygen trapper). By monitoring the concentration of this singlet oxygen trapper spectrophotometrically, the concentration of dissolved oxygen can be obtained with the established stoichiometry for the reaction between singlet oxygen and trapper. The singlet oxygen concentrations in the acrylate monomers varied from 0.59 to 2.07 × 10^?3 mol/L, depending on the monomer structure. The strategies and considerations for generalizing the method to other systems, including highly oxygenated organics, are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1285–1292, 2004     

Coherent Cooper pair tunneling in systems of Josephson junctions: Effects of quasiparticle tunneling and of the electromagnetic environment

Small capacitance tunnel junctions show single electron effects and, in the superconducting state, the coherent tunneling of Cooper pairs. We study these effects in a system of two Josephson junctions, driven by a voltage source with a finite impedance. Novel features show up in theI?V characteristics, in particular pronounced structures at subgap voltages. These are due to Cooper pair tunneling, combined with tunneling of quasiparticles or with excitation of the electromagnetic environment.     

Conducting-probe AFM nanoscale joule heating yields charge-density-wave transition detection

Several layered transition-metal dichalcogenides are studied using conducting probe AFM aiming to investigate the probe-mediated thermal processes likely to arise in the probe-substrate vicinity due to the high-current densities involved. A signature of local heating is found in the shape of current-potential (i/V) curves. The latter allows straightforward detection of a charge-density-wave (CDW) transition for 1T-TaSe(2) samples exhibiting it above room temperature. This is an illustration of a new use of conducting probe AFM to investigate solid-state bulk characteristics owing to a distinctive nanoscale Joule heating.     

Four-qubit device with mixed couplings

We present the first experimental results on a device with more than two superconducting qubits. The circuit consists of four three-junction flux qubits, with simultaneous ferro- and antiferromagnetic coupling implemented using shared Josephson junctions. Its response, which is dominated by the ground state, is characterized using low-frequency impedance measurement with a superconducting tank circuit coupled to the qubits. The results are found to be in excellent agreement with the quantum-mechanical predictions.     

Origin of Thermal and Hyperthermal CO2 from CO Oxidation on Pt Surfaces: The Role of Post‐Transition‐State Dynamics,Active Sites,and Chemisorbed CO2

The post‐transition‐state dynamics in CO oxidation on Pt surfaces are investigated using DFT‐based ab initio molecular dynamics simulations. While the initial CO₂ formed on a terrace site on Pt(111) desorbs directly, it is temporarily trapped in a chemisorption well on a Pt(332) step site. These two reaction channels thus produce CO₂ with hyperthermal and thermal velocities with drastically different angular distributions, in agreement with recent experiments (Nature, 2018 , 558, 280–283). The chemisorbed CO₂ is formed by electron transfer from the metal to the adsorbate, resulting in a bent geometry. While chemisorbed CO₂ on Pt(111) is unstable, it is stable by 0.2 eV on a Pt(332) step site. This helps explain why newly formed CO₂ produced at step sites desorbs with far lower translational energies than those formed at terraces. This work shows that steps and other defects could be potentially important in finding optimal conditions for the chemical activation and dissociation of CO₂.