Diffusion transport of aqueous solutions of alkali metal chlorides in porous glass membranes

The diffusion coefficients of lithium, sodium, potassium, and cesium chlorides in aqueous solutions in their passage through silica membranes with the pore radius r _p = 4.5–70 nm are determined over a wide range of solution concentrations. The membrane transport of the salts is discussed in terms of the structuring of the water boundary layers near the silica surface and their disruption by cations.     

Temperature dependence of the diffusion coefficient of copper(II) chloride in porous-glass membranes

Diffusion transport of a 0.5 M aqueous solution of CuCl₂ was studied in a set of porous-glass membranes with predominant pore radii of 4.5 to 70 nm in the temperature range 25–70°C. Raising the temperature causes a rise in diffusion coefficients and their gradual equalization, which eliminates their dimension dependence on the radius of membrane channels.     

Density functional theory treatment of electron correlation in the nuclear-electronic orbital approach

This paper presents the nuclear-electronic orbital density functional theory [NEO-DFT(ee)] method for including electron-electron correlation and nuclear quantum effects self-consistently in quantum chemical calculations. The NEO approach is designed to treat a relatively small number of nuclei quantum mechanically, while the remaining nuclei are treated classically. In the NEO-DFT(ee) approach, the correlated electron density is used to obtain the nuclear molecular orbitals, and the resulting nuclear density is used to obtain the correlated electron density during an iterative procedure that continues until convergence of both the nuclear and electronic densities. This approach includes feedback between the correlated electron density and the nuclear wavefunction. The application of this approach to bihalides and acetylene indicates that the nuclear quantum effects do not significantly impact the electron correlation energy, but the quantum nuclear energy is enhanced in the NEO-DFT(ee) B3LYP method. The excellent agreement of the NEO-DFT(ee)-optimized bihalide structures with the vibrationally averaged geometries from grid-based quantum dynamical methods provides validation for the NEO-DFT(ee) approach. Electron-proton correlation could be included by the development of an electron-nucleus correlation functional. Alternatively, explicit electron-proton correlation could be included directly into the NEO self-consistent-field framework with Gaussian-type geminal functions.     

Temperature-modulated differential scanning calorimetry of reversible and irreversible first-order transitions

Temperature-modulated differential scanning calorimetry of first-order transitions has led to many new observations. Some of these involve non-linear processes or deal with transformations of practically instantaneous response. The latter may cause serious lags within the calorimeter due to limited thermal conductivity of the sample and the instrument. In both cases the “reversing heat capacity” or a “complex heat capacity” is not a precise representation of the transition since both are computed from abbreviated Fourier transforms, limited to the evaluation of the first harmonic component. One has in these cases to work in the time-domain with the raw output. But even from these analyses in the time-domain many interesting new insights about the transition and the calorimeter performance can be generated.     

Electromagnetic form factor ofD * →D transition in the time-like region

The internal conversion processD ^* De ⁺ e ^–, andD ^* -pair production ine ⁺ e ^–-collisions,e ⁺ e ^– D ^* , which are described by the same electromagnetic form factor with time-like momentum transfer, have been analyzed. After carrying out a general analysis of the kinematical aspects of the one-photon mechanism has been performed and the predictions of the vector-dominance model for theD ^* D transition form factor are discussed. It is shown that use of the asymptotic behaviour of the form factors ofD ^*+,0 D ^+,0* and the theoretical values of constants ofD ^*+,0 D^+,0 radiative decay enables one to determine part of the unknown parameters of these form factors. The coefficient of the internal conversion forD ^* De ⁺ e ^– is calculated and is shown to be model independent.     

Synthesis of expanded graphdiyne substructures

Graphdiyne (1) is a member of a novel family of interesting and potentially important allotropes of carbon. Reported herein are the synthesis and spectroscopic characterization of model substructures 2-6. The macrocycles were prepared by the intramolecular cyclization of suitable alpha,omega-polyynes. Key to the success of this approach was the development of an in situ protiodesilylation/alkynylation reaction utilizing reactive phenylbutadiyne synthons. This new method has allowed for the preparation of the largest, most complete substructures of the graphdiyne network to date (3-6).     

Relationship between the ratio of ligand to metal and the coordinating ability of anions. Synthesis and structural properties of AgX-bearing bis(4-pyridyl)dimethylsilane (X- = NO2-, NO3-, CF3SO3-, and PF6-)

Studies of the anion effects on the molecular construction of a series of AgX complexes with bis(4-pyridyl)dimethylsilane (L) (X- = NO2-, NO3-, CF3SO3-, and PF6-) have been carried out. Formation of the skeletal bonds appears to be primarily associated with a suitable combination of bidentate N-donors of L and a variety of coordination geometries of Ag(I) ions. The L:Ag(I) ratios of the products are dependent on the nature of the polyatomic anions. The 1:1 adduct Ag(I)-L for NO2-, 3:4 adduct for NO3-, 2:3 adduct for CF3SO3-, and 1:2 adduct for PF6- have been obtained. A linear relationship between the ratio of ligand to metal and the coordinating ability of anions was observed. [Ag(NO2)(L)] has a unique sheet structure consisting of double helices, and [Ag3(L)4](NO3)3 is a 2 nm thick interwoven sheet structure consisting of nanotubes. The compound [Ag2(L)3](CF3SO3)2 affords a characteristic ladder-type channel structure, and [Ag(L)2](PF6) is a simple 2D grid structure.     

Low-frequency glow discharge treatment of amorphous poly(ethylene terephthalate) films

The influence of treatment in a low-frequency glow discharge on the surface properties of an amorphous poly(ethylene terephthalate) (PET) film was studied. It was shown that, at identical external discharge parameters, changes in the wettability of plasma-treated PET films depended on its morphological structure—the amorphous film had higher values of the contact angle and lower values of the surface charge density than a biaxially oriented poly(ethylene terephthalate) of the PET-E brand.     

Modeling Insurgent Dynamics Including Heterogeneity

Despite the myriad complexities inherent in human conflict, a common pattern has been identified across a wide range of modern insurgencies and terrorist campaigns involving the severity of individual events—namely an approximate power-law x ^?α with exponent α≈2.5. We recently proposed a simple toy model to explain this finding, built around the reported loose and transient nature of operational cells of insurgents or terrorists. Although it reproduces the 2.5 power-law, this toy model assumes every actor is identical. Here we generalize this toy model to incorporate individual heterogeneity while retaining the model’s analytic solvability. In the case of kinship or team rules guiding the cell dynamics, we find that this 2.5 analytic result persists—however an interesting new phase transition emerges whereby this cell distribution undergoes a transition to a phase in which the individuals become isolated and hence all the cells have spontaneously disintegrated. Apart from extending our understanding of the empirical 2.5 result for insurgencies and terrorism, this work illustrates how other statistical physics models of human grouping might usefully be generalized in order to explore the effect of diverse human social, cultural or behavioral traits.     

Special features of the state of copper(II) oxide and its electric conductivity in porous glass

Controllable accumulation of copper(II) oxide in porous glass was carried out by repeated impregnation of the carrier by Cu(NO₃)₂ aqueous solutions with subsequent thermal decomposition of the salt. The results of measuring electric conductivity of a series of modified plates in combination with the data on the optical and X-ray electron spectroscopy make it possible to characterize two trends in the oxide distribution on a silica surface. In the case of its cyclic accumulation by small portions, a two-dimensional structure of monolayer filling the surface is presumably formed in a narrow range of CuO concentration, whereas the increase in the ??step?? of the accumulation gives rise to the formation and growth of island oxide particles.