Rotational viscosity of uniaxial molecules

Non-equilibrium molecular dynamics (NEMD) are used to calculate the vortex or rotational viscosity of fluids composed of uniaxial molecules. It is shown that the NEMD homogeneous spin flow algorithm proposed by Edberg, R., Evans, D. J., and Moriss, G. P., 1987, Molec. Phys., 62, 1357 considerably underestimates the vortex viscosity. A modified version of this algorithm is proposed and applied to liquid chlorine and nitrogen. The results are in good agreement with previous work using equilibrium or other NEMD methods, and also show that at high spin rates the vortex viscosity decreases with increase in magnitude of the external torque used to drive the spin flow.     

THE HADAMARD INEQUALITY FOR CONVEX FUNCTION VIA FRACTIONAL INTEGRALS

In this paper, we establish several inequalities for some differantiable mappings that are connected with the Riemann-Liouville fractional integrals. The analysis used in the proofs is fairly elementar...     

On the role of the definition of potential models in Gibbs ensemble phase equilibria simulations of the H2S-pentane mixture

The effect of treating explicitly the coulombic and polarization interactions is investigated through the calculation of the coexistence curve of the pentane-H₂S binary mixture. In this work, potential models have been developed for hydrogen sulphide and pentane, which include electrostatic sites—estimated from ab initio calculations—and polarizable sites—estimated from experimental data—in addition to Lennard-Jones sites. Compared to existing models, these new models have the same number of fitting parameters to experimental thermodynamic data. They are shown to correctly describe the coexistence curve of the pure compounds. When applied to the case of mixtures, together with Lorentz-Berthelot combining rules, they allow one to obtain a more accurate prediction of the coexisting compositions of the mixture. Furthermore, it is shown that the interaction energy in this kind of mixture cannot be properly described by using effective potential models usually considered for pure compounds.     

Three-dimensional packing structure and electronic properties of biaxially oriented poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) films

We use a systematic approach that combines experimental X-ray diffraction (XRD) and computational modeling based on molecular mechanics and two-dimensional XRD simulations to develop a detailed model of the molecular-scale packing structure of poly(2,5-bis (3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT-C(14)) films. Both uniaxially and biaxially aligned films are used in this comparison and lead to an improved understanding of the molecular-scale orientation and crystal structure. We then examine how individual polymer components (i.e., conjugated backbone and alkyl side chains) contribute to the complete diffraction pattern, and how modest changes to a particular component orientation (e.g., backbone or side-chain tilt) influence the diffraction pattern. The effects on the polymer crystal structure of varying the alkyl side-chain length from C(12) to C(14) and C(16) are also studied. The accurate determination of the three-dimensional polymer structure allows us to examine the PBTTT electronic band structure and intermolecular electronic couplings (transfer integrals) as a function of alkyl side-chain length. This combination of theoretical and experimental techniques proves to be an important tool to help establish the relationship between the structural and electronic properties of polymer thin films.     

A redox series of gallium(III) complexes: ligand-based two-electron oxidation affords a gallium-thiolate complex

We have prepared a series of gallium(III) complexes of the redox active iminopyridine ligand (IP). Reaction of GaCl(3) with iminopyridine ligand (IP) in the presence of either two or four equivalents of sodium metal resulted in the formation of deep green (IP(-))(2)GaCl (1), or deep purple [(DME)(3)Na][(IP(2-))(2)Ga] (2a), respectively. Complex 1 is paramagnetic with a room temperature magnetic moment of 2.3 μ(B) which falls to 0.5 μ(B) at 5 K. These observations indicate that two ligand radicals comprise a triplet at room temperature which becomes a singlet due to antiferromagnetic coupling at low temperature. Complex 2 is diamagnetic. Cyclic voltammograms recorded on 0.3 M Bu(4)NPF(6) THF solutions of [Na(THF)(6)][(IP(2-))(2)Ga](-) (2b) indicate that oxidation of 2b occurs in two two-electron steps at -1.31 V and -0.54 V vs. SCE. The observation of two-electron redox events indicates that electronic coupling through the gallium(III) center is minimal and that the two IP ligand on 2b are oxidized concurrently. Oxidation of 2 with one equivalent of MeS-SMe afforded the two-electron oxidized product (IP(-))(2)Ga(SMe) (3). This complex has an electronic structure analogous to 1. Accordingly, both 1 and 3 are deep green in color and magnetic susceptibility measurements performed on 3 confirm the triplet character of the complex at room temperature. Electron paramagnetic resonance experiments on 1 and 3 display a quartet signal at g = 2.0 which confirmed the triplet nature of the compounds, and a half field signal consistent with the integer spin state.     

Confined cubic blue phases under shear

We study the behaviour of confined cubic blue phases under shear flow via lattice Boltzmann simulations. We focus on the two experimentally observed phases, blue phase I and blue phase II. The disclination network of blue phase II continuously breaks and reforms under shear, leading to an oscillatory stress response in time. The oscillations are only regular for very thin samples. For thicker samples, the shear leads to a 'stick-slip' motion of part of the network along the vorticity direction. Blue phase I responds very differently: its defect network undergoes seemingly chaotic rearrangements under shear, irrespective of system size.     

Beam-target double-spin asymmetry A{LT} in charged pion production from deep inelastic scattering on a transversely polarized {3}He target at 1.4<Q{2}<2.7 GeV{2}

We report the first measurement of the double-spin asymmetry A{LT} for charged pion electroproduction in semi-inclusive deep-inelastic electron scattering on a transversely polarized {3}He target. The kinematics focused on the valence quark region, 0.16相似文献   

How to prepare and stabilize very small nanoemulsions

Practical and theoretical considerations that apply when aiming to formulate by ultrasonication very small nanoemulsions (particle diameter up to 150 nm) with very high stability are presented and discussed. The droplet size evolution during sonication can be described by a monoexponential function of the sonication time, the characteristic time scale depending essentially on the applied power. A unique master curve is obtained when plotting the mean diameter size evolution as a function of sonication energy. We then show that Ostwald ripening remains the main destabilization mechanism whereas coalescence can be easily prevented due to the nanometric size of droplets. The incorporation of "trapped species" within the droplet interior is able to counteract Ostwald ripening, and this concept can be extended to the membrane compartment. We finally clarify that nanoemulsions are not thermodynamically stable systems, even in the case where their composition lies very close to the demixing line of a thermodynamically stable microemulsion domain. However, as exemplified in the present work, nanoemulsion systems can present very long-term kinetic stability.     

Granulation and bistability in non-Brownian suspensions

In granulation, a dense colloidal suspension is converted into pasty lumps by application of flow. Often, such lumps are bistable: each can exist either as a fluid droplet (with a shiny surface) or as a jammed granule, whose rough surface creates a bulk stress via capillary action. Such bistability can be explained if the bulk steady-state flow curve is sufficiently nonmonotonic that, above some threshold of stress, flow ceases entirely. This is a stronger condition than the one required to see discontinuous shear thickening, but closely related to it. For instance, inertia can play a role in shear thickening, but not in static bistability. Suitable flow curves were previously found in a phenomenological model of the colloidal glass transition, in which Brownian motion is arrested at high stresses. However, granulation often involves particles too large for Brownian motion to be significant, so that another nonmonotonicity mechanism is needed. A very recent theory, in which the proportion of frictional rather than lubricated contacts increases with stress, provides just such a mechanism, and we use it here to give a simple explanation of granular bistability in non-Brownian suspensions, which requires knowledge only of the steady-state flow curve. However, jamming is in general a history-dependent phenomenon which allows bistability to arise under broader conditions than those just described, possibly including systems that do not shear-thicken at all. In this paper, we focus on explanations of granular bistability based on steady-state shear-thickening, but also discuss alternative explanations based on flow history effects.     

P-N COMPOUNDS 28. PHOSPHAMINIMIDES 3. 4-NITROBENZYLATION OF PHOSPHINYL-1, 1-DIMETHYL HYDRAZIDES AND FORMATION OF A UNIQUE HYDRAZINIUM INNER SALT1

Abstract

The treatment of diethoxyphosphinyl-1,1-dimethylhydrazide with 4-nitrobenzylbromide at 82–90°C resulted in the loss of EtBr and the formation of EtO(^?O)P(O) NHN⁺(CH₃)₂CH₂-4-NO₂Ph, a novel type of phosphaminimide. At lower temperatures the diethoxyhydrazide gave the hydrazinium bromide which slowly underwent loss of EtBr to yield the same product. The diphenoxy compound similarly lost HBr at high, but not lower, temperature with production of the normal phosphaminimide. The diphenyl derivative yielded the expected hydrazinium bromide which was dehydrobrominated to the usual phosphaminide with NaOH. The reaction between all three hydrazides and iodomethane, followed by dehydroiodination, gave the usual phosphaminimides.