Pressure dependence of the second virial coefficient of dilute polystyrene solutions

The pressure derivatives of the second virial coefficients [dA₂/dP; 0.1 ≤ P (MPa) ≤ 35.0] for dilute polystyrene (PS) solutions in good, θ, and poor solvents were measured with static light scattering. The solvent quality improved (dA₂/dP > 0) in the good and poor solvents that we investigated (toluene, chloroform; and methylcyclohexane) but deteriorated (dA₂/dP < 0) in θ solvents (cyclohexane and 50‐50 cis,trans‐decalin). The effects of temperature [22 < T (°C) < 45] and molecular weight [25 × 10³ < weight‐average molecular weight (amu mol^?1) < 900 × 10³] on dA₂/dP for PS/cyclohexane solutions were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3070–3076, 2003     

Non-iterative and exact method for constraining particles in a linear geometry

We present a practical numerical method for evaluating the Lagrange multipliers necessary for maintaining a constrained linear geometry of particles in dynamical simulations. The method involves no iterations and is limited in accuracy only by the numerical methods for solving small systems of linear equations. As a result of the non-iterative and exact (within numerical accuracy) nature of the procedure, there is no drift in the constrained geometry, and the method is therefore readily applied to molecular dynamics simulations of, for example, rigid linear molecules or materials of non-spherical grains. We illustrate the approach through implementation in the commonly used second-order velocity-explicit Verlet method. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 911-916, 2005     

Conformational behavior of nylon 6 in mixed solvents

The intrinsic viscosity [η], Huggins constant (K_H), laser light scattering, UV and IR measurements of Nylon 6 are made in m‐cresol and its mixture with 1,4‐dioxane at 20–60 °C. The intrinsic viscosity, R_g, A₂, (<S>²)^1/2 (calculated from viscosity data), R_H, and UV absorbance initially increase and then decrease with the rise in 1,4‐dioxane contents. The K_H and the transmittance of ? OH group in IR spectra show an opposite trend to that of [η]. The dielectric constant calculated from the refractive index of the solvent (m‐cresol with 1,4‐dioxane) and polymer solution shows a continuous decrease with the amount of 1,4‐dioxane. Activation energy shows a minimum while linear expansion coefficient (α³) maximum with the addition of 1,4‐dioxane. Change in [η], K_H, and other characteristics of the polymer solutions with alterations in solvent composition and temperature are the result of variation in the thermodynamic quality of the solvent, its selective adsorption, hydrogen bonding, and conformational transitions. It has been concluded that the addition of 1,4‐dioxane first enhances the quality of the solvent, encourages hydrogen bonding, and specific adsorption, and then deteriorates, bringing conformational transitions in the polymer molecules. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 534–541, 2005     

ATP-dependent active transport simulations based on a phosphatase-channel-kinase membrane structure

Simulations of coupled interactions involving enzymatic reaction diffusion and electrostatic interactions were conducted under a fixed phosphatase-channel-kinase (PCK) topology oriented from the outside to the inside of a charged membrane structure. Depending on the phosphatase and kinase locations, we recently demonstrated that active transport of a phosphorylated substrate may occur via this PCK topology. The present analysis demonstrates that, if in addition to this topology, a phosphatase activity (P(1)) is also present on the inner side of the membrane, but outside the unstirred layer surrounding the inner membrane surface, then active transport of the corresponding unphosphorylated substrate may also occur. Therefore, this PCK membrane topology, which behaves as a specific ATP-dependent transporter, appears as a general topology permitting; first, on its own the active transport of a phosphorylated substrate; second, when associated with a phosphatase acting in the bulk of the receiver compartment, the active transport of the corresponding unphosphorylated substrate, that is, in most cases, the transport of an uncharged substrate. The general mathematical model given permits the active transport of a phosphorylated substrate to be analyzed (in the absence of P(1)), the active transport of an unphosphorylated substrate (in the presence of P(1)), whatever the charge distributions on both sides of the membrane surface and whatever the positions of the membrane-bound phosphatase and the membrane-bound kinase. This general model also takes into account the consumption of ATP occurring into the receiver compartment during the time course of these transport phenomena. A broad analysis of the role played by the main parameters taken into account in the model was conducted to precisely define the physicochemical conditions and the membrane topology needed for the highest active transports within the shortest time.     

Normal Liquid Helium-3 in the Static Fluctuation Approximation

In this paper normal liquid helium-3 is studied for the first time within the framework of the so-called static fluctuation approximation. This is based on the replacement of the square of the local-field operator with its mean value. A closed set of nonlinear integral equations is derived for neutral many-fermionic systems. This set is solved numerically by an iteration method for a realistic interhelium potential. The thermodynamic properties are then obtained for normal liquid helium-3. The quadratic-fluctuation approximation is found to be valid for this system in the low-temperature limit (0.25 K). Our results are presented in a set of figures. The role of the interaction is emphasized, and the functional dependence on the temperature of key thermodynamic quantities is derived for normal liquid helium-3.     

Design of chirped Mo/Si multilayer mirror in the extreme ultraviolet region

The chirped Mo/Si multilayer mirror in the extreme ultraviolet region is designed to obtain sub-femtosecond pulses from high-order harmonics. Numerical simulations of temporal profile of the pulses are made for superposition of incident high-order harmonics and that of reflected ones by the chirped multilayer mirror.The normal incidence reflectivity and chirp in the wavelength range of 12.5 - 16.5 nm are 6.7% ±0.5%and-3617±171 as2, respectively. Simulation results indicate that the designed chirped multilayer mirror can be used for producing 104-as pulses.     

Hydrated electron: Nonempirical cluster approach

Interface water anions composed of several chainlike or cyclic fragments were simulated with a 6‐31++G** basis set at the unrestricted Hartree–Fock level with the second‐order Moeller–Plesset perturbation theory corrections taken into account. The estimated vertical electron detachment energies (VDEs) of (H₂O) anions were approximated by a VDE‐n^?1/3 dependence close to the experimental one. A hypothesis about the predominant formation of interface structures under conditions of molecular flows is put forward. The atomic population analysis, character of the highest occupied molecular orbital, and changes in the geometry of interface anions with an increase in their molecular size reveal the compact localization of the excess electron density in water clusters and allow evaluating the effective excess‐electron radius of condensed water as 2.5 Å, in good agreement with a similar empirical estimate. The scope of the data obtained shows the relatively low probability of the formation of octahedral hydration shells compared to the tetrahedral coordination of solvating water molecules. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Calculation of anisotropic strain-engineered patterns of monolayer islands

The self-organization of monolayer epitaxy islands in presence of anisotropies in surface stress, applied stress, and lattice mismatch between the film and substrate materials is investigated. The fundamental nature of island interactions is addressed in the context of a model wherein the system free energy consists of the excess energy and strain energy of atomic surface steps. It is shown the anisotropy can change the character of island interactions. An energy-reducing kinetic relation is adopted to evolve an initially random morphology towards a generally metastable minimum energy state. It is found the self-organization of islands into a regular array requires both the repulsion between islands and tendency for islands to aligned in a particular direction. Small anisotropies provide the required repulsion but not the tendency for islands to align and large anisotropies provide the necessary alignment but cause islands to attract. Modest levels of anisotropy provide the most favorable conditions of self-organization.     

Blocking effects in irreversible adsorption of linear macromolecules

A new variant of random sequential adsorption (RSA), namely random sequential ballistic adsorption (RSBA), is proposed to explore the possible role of blocking effects in the adsorption dynamics of ballistically arriving objects. These objects upon adsorption can protrude outside the substrate and in turn can obstruct and hence reject the adsorption of newly arriving objects. Adsorption of linear macromolecules (modeled as infinitesimally thin needles), on a two-dimensional continuum substrate is studied using RSBA model. It is shown analytically that in late time regime, the number n(t) of adsorbed objects at time t follows a power law n(t) ∼ t^α, as in RSA, but with a different exponent, α = 2/3. Computer simulations are also carried out. The simulation results are found to be in close agreement with the analytical results. The exponent behavior for real experimental conditions is also analyzed.     

A universal algorithm for calculating the backscattering factor in Auger-electron spectroscopy

We describe a universal Monte Carlo algorithm that can be used for the efficient calculation of backscattering factors (BFs) for quantitative Auger-electron spectroscopy (AES). This algorithm makes use of the continuous slowing-down approximation and the electron stopping power instead of simulation of individual inelastic-scattering events. This approach is attractive because it can be applied to any material with an empirical formula for the stopping power, available data for differential elastic-scattering cross sections, and an empirical formula for inner-shell ionization cross sections. We report BFs for the Si KL₂₃L₂₃, Cu L₃M₄₅M₄₅, Ag M₅N₄₅N₄₅, and Au M₅N₆₇N₆₇ Auger transitions in the corresponding elemental solids. These BFs were calculated for normal incidence of the primary beam, primary energies from near threshold for ionization of the relevant core levels to 20 keV, and Auger-electron emission angles of 10°, 60°, and 80°. We found satisfactory agreement between these BFs and values obtained from a more accurate algorithm in which individual inelastic-scattering events were simulated. Percentage deviations between BFs from the two algorithms were <2% for Au, <5% for Ag, <7% for Cu, and <10% for Si for primary energies likely to be used in practical AES. These deviations arise mainly from our use of stopping powers from the empirical formula rather than more reliable values calculated from experimental optical data.