Rovibrational and energetic analysis of the hydroxyethynyl anion (CCOH−)

For the first time, high-level structural and rovibrational data are provided for the hyroxyethynyl anion, CCOH^?. CCOH^? is a promising molecule for interstellar detection even though no new anions have been observed in the interstellar medium for the past half-decade. The large dipole moment of the corresponding neutral radical may be key for its creation as has been hypothesised and supported for other anions known to exist in various astronomical environments. Highly accurate quartic force fields are employed where previous benchmarks have produced spectroscopic constants and anharmonic vibrational frequencies within 20 MHz and 1 cm^?1, respectively, of experiment. This same approach is applied here for CCOH^? and its deuterated isotopologue with the goal of assisting laboratory experiments and/or astronomical observers in the potential detection of this anion.     

Nonstationarity and related measures for time‐dependent hartree–fock and multiconfigurational models

Based on an earlier article (Eberly and Singh, Phys. Rev. D 1973 , 7, 359) and related works on short‐time evolution, this article proposes a many‐electron formulation for the nonstationarity degree which can be assigned to quantum system at each time point. The key measure introduced, , is a nonstationarity index that can be thought of as an inverse nominal lifetime at each instance of time. The index is directly computed from the time derivative of one‐electron density matrix and is a size‐consistent quantity. In this article, the approach is developed for the time‐dependent Hartree–Fock (TDHF), single‐excitation (TDCIS), and time‐dependent full configuration interaction (TDFCI) models. As a rule, nonstationarity effects are more pronounced in correlated electron systems, and a joint analysis of and the multiconfigurational character of wave functions apparently provide a deeper insight into dynamical molecular processes. The performed calculations on small molecules in laser fields show a preference for the TDCIS model when comparing TDCIS and TDHF with the “exact” TDFCI model. © 2013 Wiley Periodicals, Inc.     

Effect of Inorganic Solids,Wax to Asphaltene Ratio,and Water Cut on the Stability of Water-in-Crude Oil Emulsions

The formation of stable water-in-crude oil emulsions during petroleum production and refinery may create sever and costly separation problems. It is very important to understand the mechanism and factors contributing to the formation and stabilization of such emulsions for both great economic and environmental development. This article investigates some of the factors controlling the stability of water-in-crude oil emulsions formed in Burgan oil field in Kuwait. Water-in-crude oil emulsion samples collected from Burgan oil filed have been used to separate asphaltenes, resins, waxes, and crude oil fractions. These fractions were used to prepare emulsion samples to study the effect of solid particles (Fe₃O₄) on the stability of emulsions samples. Results indicate that high solid content lead to higher degree of emulsion stability. Stability of emulsion samples under various waxes to asphaltenes (W/A) ratios have also been tested. These tests showed that at low W/A content, the emulsions were very stable. While at a wax to asphaltene ratio above 1 to 1, the addition of wax reduced emulsion stability. Stability of emulsion samples with varying amount of water cut has also been investigated. Results indicated that stability and hence viscosity of emulsion increases as a function of increasing the water cut until it reaches the inversion point where a sharp decline in viscosity takes place. This inversion point was found to be approximately at 50% water cut for the crude oils considered in this study.     

MICELLE FORMATION BY ANIONIC AND CATIONIC SURFACTANTS IN AQUEOUS 18-CROWN-6 ETHER,P-CYCLODEXTRIN,AND 1,10-PHENANTHROLINE SOLUTIONS AT DIFFERENT TEMPERATURES

The conductances of sodium perfluorooctanoate (SPFO), sodium dodecylsulphate (SDS), dodecyltrimethylammonium bromide (DTAB), and tetradecyltrimethylammonium bromide (TTAB) in 18-crown-6 ether + water (CR+W), p-cyclodextrin + water (CY+W), and 1,10-phenanthroIine + water (Phen+W) mixtures with fixed 4 mM of each additive were determined over the temperature range of 5-55 °C. The conductivity plots for all the surfactants showed single break from which the critical micellization concentration (cmc) and degree of micelle ionization (x) were computed. From the pre and the post micellar slopes of the conductivity curves, the equivalent conductivities of the monomeric (Aass) and the micellar states (Amjc), respectively, were calculated and discussed with respect to the surfactant-additive complexation. It was observed that the micelle formation of all the ionic surfactants irrespective of the nature of their head groups were delayed in CYC+W in comparison to that in CR+W and Phen+W systems over the temperature range studied. The micelle formation of SPFO and SDS in CR+W and Phen+W systems showed stabilization of the respective micelles due to the adsorption of Na⁺-CR and Na+-Phen complexes at the micelle solution interface in comparison to that of DTAB and TTAB.     

Microstructure and Magnetic Properties of Carbon‐Coated Nanoparticles

Abstract

In the present work, microstructure and superparamagnetic properties of two types of carbon‐coated magnetic Ni and Fe nanoparticles [Ni(C) and Fe(C)] are reviewed. High‐resolution transmission electron microscopy (HRTEM), electron diffraction (SAED), and x‐ray diffraction (XRD) analyses have been used to reveal the distinct structural morphologies of Ni and Fe nanoparticles. Moreover, novel carbon‐coated Ni nanoparticle assemblies offer us great opportunities for studying the mechanism of superparamagnetism in particle assemblies. Magnetization measurements [M(T) and M(H) curves] for assemblies of Ni nanoparticles indicate that modified superparamagnetic properties at T > T _B, have been found in the assemblies of Ni(C) particles. The blocking temperature, T _B, is determined to be near 115K under a certain applied field. Above T _B, the magnetization M(H, T) can be described by the classical Langevin function L using the relation, M/M _s (T = 0) = coth (μH/kT) ? kT/μH. It is suggested that these assemblies of carbon‐coated Ni nanoparticles have typical single‐domain, field‐dependent superparamagnetic relaxation properties. Finally, Mössbauer spectra and hyperfine magnetic fields at room temperature for the assemblies of Fe(C) nanoparticles confirm their distinct nanophases that were detected by structural analysis. Modified superparamagnetic relaxation is observed in the assemblies of Fe(C) nanoparticles, which is attributed to the nanocrystalline nature of the carbon‐coated nanoparticles.     

Water‐in‐Crude Oil Emulsions in the Burgan Oilfield: Effects of Oil Aromaticity,Resins to Asphaltenes Content (R/(R+A)), and Water pH

Asphaltenes and resins separated from emulsion samples collected from Burgan oil field were used with heptane‐toluene mixtures as model oil to study the effect of oil aromaticity, resin content, and pH of the aqueous phase on the stability of water in model emulsions. It was confirmed that, as long as the asphaltenes are completely solubilized, increasing aromaticity leads to less stable emulsions. A consistent correlation between emulsion stability and relative resin mass content (R/(R+A)) was observed for all three of the field samples. There was a sharp decrease in stability when the R/(R+A) value exceeded 0.75. Emulsion stability was enhanced at high pH and possibly at very low pH (<2).     

Electro‐optic switching with liquid crystal graphene

Graphene oxide (GO) particles in aqueous dispersions can form liquid crystal (LC) phases at extremely low concentrations due to the extremely high aspect ratio of the flakes and noticeably, they possess an extremely large Kerr coefficient attractive for low power consumption electro‐optic devices. Reduced graphene does not easily form LC phases in water due to its hydrophobic nature but here we show that stable dispersions of reduced graphene oxide can be realized with surfactants and that they exhibit birefringence upon shearing as well as under application of electric fields. The performance of the system is largely superior to GO LC possessing longer time stability and drastically improved electro‐optic properties with an induced birefringence twice as large at the same field strength thanks to the almost recovery of graphene properties upon reduction. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Stability of AgIII towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron Ag^I/Ag^III processes is currently emerging. However, the range of stability of the required and uncommon Ag^III species is virtually unknown. Here, the stability of Ag^III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]⁻ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag^III−X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh₄][(CF₃)₃AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃Ag(N₃)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]⁻ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSⁿ). The experimental detection of the two series of mixed complexes [CF₃AgX]⁻ and [FAgX]⁻ arising from the corresponding parent species [(CF₃)₃AgX]⁻ demonstrate that the Ag−X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of Ag^III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.     

Numerically anticanonical divisors on Kato surfaces

The compact curves of an intermediate Kato surface $S$ form a basis of $H^2(S,\mathbb{Q})$. We present a way to compute the associated rational coefficients of the first Chern class $c_1\left(S\right)$. We get in particular a simple geometric obstruction for $c_1\left(S\right)$ to be an integral class, or equivalently index $\left(S\right)=1$. In the final part we discuss relations with some recent work of Dloussky (2011) and Oeljeklaus and Toma (2009).     

Surface-Plasmonic-Field-Induced Photoredox Catalysis and Mediated Electron Transfer for Washing-Free DNA Detection

Distance-dependent electromagnetic radiation and electron transfer have been commonly employed in washing-free fluorescence and electrochemical bioassays, respectively. In this study, we combined the two distance-dependent phenomena for sensitive washing-free DNA detection. A distance-dependent surface plasmonic field induces rapid photoredox catalysis of surface-bound catalytic labels, and distance-dependent mediated electron transfer allows for rapid electron transfer from the surface-bound labels to the electrode. An optimal system consists of a chemically reversible acceptor (Ru(NH₃)₆³⁺), a chemically reversible photoredox catalyst (eosin Y), and a chemically irreversible donor (triethanolamine). Side reactions with O₂ do not significantly decrease the efficiency of photoredox catalysis. Energy transfer quenching between the electrode and the label can be lowered by increasing the distance between them. Washing-free DNA detection had a detection limit of approximately 0.3 nm in buffer and 0.4 nm in serum without a washing step.