A photoelectric study on the interface between metallic silver and vitreous As2S3

The electrostatic potential at the AgAs₂S₃ interface was investigated. In the dark, cells of a structure, Ag/As₂S₃/Al behaved like and an electrochemical battery. When light fell onto the cells, short-circuit currents were observed, but their appearancesvaried much, depending on the excitation wavelength and the material of the illuminated electrode. At wavelengths longer than the absorption edge of As₂S₃ glass, photocurrents were characteristic of the polarization current and little influenced by the external field. A model for explaining these findings was proposed on an assumption of an interface reaation between silver and vitreous As₂S₃ in the dark. The interfacial reaction was supposed to accompany a charge separation leading to formation of a potential barrier at the interface.     

Estimation of parameters for discretely observed diffusion processes with a variety of rates for information

A specific form of stochastic differential equation with unknown parameters are considered. We do not necessarily assume ergodicity or recurrency, and any moment conditions for the true process, but some tightness conditions for an information-like quantity. The interest is to estimate the parameters from discrete observations the step size of which tends to zero. Consistency and the rate of convergence of proposed estimators are presented. The rate is deduced naturally from the rate for the information-like quantities.     

Stable meso–meso-Linked 2NH-Corrole Radical Dimers as a Key Intermediate to Corrole Tape

While oxidation of 5,5′,15,15′-tetramesityl-10-10′-linked 3NH-corrole dimer with DDQ gave the corresponding triply linked 2NH-corrole tape, the use of an equimolar amount of p-chloranil as a milder oxidant resulted in the formation of a 10-10′-linked neutral 2NH-corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10-10′-linked bis-pyridine-coordinated Co^III corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.     

Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach

Lithium phosphorus oxynitride (LiPON) is an amorphous solid-state lithium ion conductor displaying exemplary cyclability against lithium metal anodes. There is no definitive explanation for this stability due to the limited understanding of the structure of LiPON. Herein, we provide a structural model of RF-sputtered LiPON. Information about the short-range structure results from 1D and 2D solid-state NMR experiments. These results are compared with first principles chemical shielding calculations of Li-P-O/N crystals and ab initio molecular dynamics-generated amorphous LiPON models to unequivocally identify the glassy structure as primarily isolated phosphate monomers with N incorporated in both apical and as bridging sites in phosphate dimers. Structural results suggest LiPON′s stability is a result of its glassy character. Free-standing LiPON films are produced that exhibit a high degree of flexibility, highlighting the unique mechanical properties of glassy materials.     

Cyclophane‐Type Chlorin Dimers from Dynamic Covalent Chemistry of 2,18‐Porphyrinyl Dicyanomethyl Diradicals

2,18‐Bis(dicyanomethyl)‐substituted Ni^II porphyrin 8 and Zn^II porphyrin 11 were prepared and subjected to oxidation with PbO₂ in CH₂Cl₂ at 298 K to give cyclophane‐type chlorin dimers ( 9 )₂ and ( 12 )₂ as a consequence of double recombination of biradicals 9 and 12 , respectively. Dimer ( 9 )₂ takes a syn‐conformation of two distorted Ni^II chlorins but ( 12 )₂ takes an anti‐conformation of relatively planar Zn^II chlorins. At 298 K, dimer ( 9 )₂ is stable and its ¹H NMR spectrum is sharp but becomes broad at high temperature, while the ¹H NMR spectrum of ( 12 )₂ is considerably broad even at 298 K but becomes sharper at low temperature. These results indicate that the chlorin dimers dissociate to radical species, but the activation barrier of the dissociation of ( 12 )₂ is much less than that of ( 9 )₂. The involvement of diradicals in dynamic covalent chemistry has been suggested by thermal scrambling of hetero dimer ( 16 )₂ to give homo dimers ( 9 )₂ and ( 15 )₂.     

Solution property preserving reconstruction for finite volume scheme: a boundary variation diminishing+multidimensional optimal order detection framework

The purpose of this work is to build a general framework to reconstruct the underlying fields within a finite volume (FV) scheme solving a hyperbolic system of PDEs (Partial Differential Equations). In an FV context, the data are piecewise constants per computational cell and the physical fields are reconstructed taking into account neighbor cell values. These reconstructions are further used to evaluate the physical states usually used to feed a Riemann solver which computes the associated numerical fluxes. The physical field reconstructions must obey some properties linked to the system of PDEs such as the positivity, but also some numerically based ones, like an essentially nonoscillatory behavior. Moreover, the reconstructions should be highly accurate for smooth flows and robust/stable for discontinuous solutions. To ensure a solution property preserving reconstruction, we introduce a methodology to blend high-/low-order polynomials and hyperbolic tangent reconstructions. A boundary variation diminishing algorithm is employed to select the best reconstruction in each cell. An a posteriori MOOD detection procedure is employed to ensure the positivity by recomputing the rare problematic cells using a robust first-order FV scheme. We illustrate the performance of the proposed scheme via the numerical simulations for some benchmark tests which involve vacuum or near vacuum states, strong discontinuities, and also smooth flows. The proposed scheme maintains high accuracy on smooth profile, preserves the positivity and can eliminate the oscillations in the vicinity of discontinuities while maintaining sharper discontinuity with superior solution quality compared to classical highly accurate FV schemes.     

Porphyrin-Stabilized Nitrenium Dication

An azepine-fused Ni^II-porphyrin dimer was synthesized by oxidative amination of β–β linked Ni^II-porphyrin dimer, and its N-aryl congener was synthesized by twofold Buchwald–Hartwig amination of β-to-β linked and dichlorinated Ni^II-porphyrin dimer. Oxidation of the NH congener gave neutral aminyl radical and nitrenium ion successively in a similar manner to the previously reported NH-bridged Ni^II-porphyrin dimer. Oxidation of the N-aryl congener afforded formal nitrenium dication in a single-step two-electron oxidation. Stable nitrenium dications that are isoelectronic to neutral trivalent boron compounds and tertiary carbocations are rare. The chemical stability of the nitrenium dication was improved by chlorine substitution at the most reactive β-position. The structural, optical, magnetic, electrochemical properties of these compounds were fully characterized.