Structure, energetics and diffusion properties of isomers of trimethyl benzene in beta zeolite: Uptake and Monte Carlo simulation study

A Monte Carlo study along with experimental uptake measurements of 1,2,3-trimethyl benzene, 1,2,4-trimethyl benzene and 1,3,5-trimethyl benzene (TMB) in beta zeolite is reported. The TraPPE potential has been employed for hydrocarbon interaction and harmonic potential of Demontis for modeling framework of the zeolite. Structure, energetics and dynamics of TMB in zeolite beta from Monte Carlo runs reveal interesting information about the diameter, properties of these isomers on confinement. Of the three isomers, 135TMB is supposed to have the largest diameter. It is seen TraPPE with Demontis potential predicts a restricted motion of 135TMB in the channels of zeolite beta.Experimentally, 135TMB has the highest transport diffusivity whereas MID results suggest this has the lowest self diffusivity. (C) 2009 Elsevier Inc. Ail rights reserved.

Dynamics of dense sheared granular flows. Part 1. Structure and diffusion

Shear flows of inelastic spheres in three dimensions in the Volume fraction range 0.4-0.64 are analysed using event-driven simulations.Particle interactions are considered to be due to instantaneous binary collisions, and the collision model has a normal coefficient of restitution e(n) (negative of the ratio of the post- and pre-collisional relative velocities of the particles along the line joining the centres) and a tangential coefficient of restitution e(t) (negative of the ratio of post- and pre-collisional velocities perpendicular to the line Joining the centres). Here, we have considered both e(t) = +1 and e(t) = e(n) (rough particles) and e(t) =-1 (smooth particles), and the normal coefficient of restitution e(n) was varied in the range 0.6-0.98. Care was taken to avoid inelastic collapse and ensure there are no particle overlaps during the simulation. First, we studied the ordering in the system by examining the icosahedral order parameter Q(6) in three dimensions and the planar order parameter q(6) in the plane perpendicular to the gradient direction. It was found that for shear flows of sufficiently large size, the system Continues to be in the random state, with Q(6) and q(6) close to 0, even for volume fractions between phi = 0.5 and phi = 0.6; in contrast, for a system of elastic particles in the absence of shear, the system orders (crystallizes) at phi = 0.49. This indicates that the shear flow prevents ordering in a system of sufficiently large size. In a shear flow of inelastic particles, the strain rate and the temperature are related through the energy balance equation, and all time scales can be non-dimensionalized by the inverse of the strain rate. Therefore, the dynamics of the system are determined only by the volume fraction and the coefficients of restitution. The variation of the collision frequency with volume fraction and coefficient of estitution was examined. It was found, by plotting the inverse of the collision frequency as a function of volume fraction, that the collision frequency at constant strain rate diverges at a volume fraction phi(ad) (volume fraction for arrested dynamics) which is lower than the random close-packing Volume fraction 0.64 in the absence of shear. The volume fraction phi(ad) decreases as the coefficient of restitution is decreased from e(n) = 1; phi(ad) has a minimum of about 0.585 for coefficient of restitution e(n) in the range 0.6-0.8 for rough particles and is slightly larger for smooth particles. It is found that the dissipation rate and all components of the stress diverge proportional to the collision frequency in the close-packing limit. The qualitative behaviour of the increase in the stress and dissipation rate are well Captured by results derived from kinetic theory, but the quantitative agreement is lacking even if the collision frequency obtained from simulations is used to calculate the pair correlation function used In the theory.

Investigation of surface activity and photoinduced diffusion of metals in solution deposited amorphous films of As2S3

Surface activity of solution deposited (SD) amorphous films of As2S3 has been investigated. Silver and copper are readily deposited on such films from appropriate aqueous ionic solutions. The metals diffuse into the films upon irradiation with energetic photons. Structure and properties of SD films have been investigated using electron microscopy, optical spectroscopy and differential scanning calorimetry. The amorphous films tend to crystallize upon metal diffusion. The stability of amorphous films, the deposition of metals on their active surfaces and the photo-induced diffusion may all be attributed to the presence or production of charged defects in amorphous chalcogenide films.

Quantum diffusion in thin disordered wires

Quantum Ohmic residual resistance of a thin disordered wire, approximated as a one-dimensional multichannel conductor, is known to scale exponentially with length. This nonadditivity is shown to imply (i) a low-frequency noise-power spectrum proportional to -ln(Ω)/Ω, and (ii) a dispersive capacitative impedance proportional to tanh(√iΩ )/ √iΩ. A deep connection to the quantum Brownian motion with linear dynamical frictional coupling to a harmonic-oscillator bath is pointed out and interpreted in physical terms.

Prediction of Intrinsic kinetics in diffusion disguised immobilized enzyme systems

When immobilized enzyme kinetics are disguised by inter- and intraparticle diffusion effects, an approximate mathematical procedure is indicated whereby experimental data obtained in the limiting ranges of first- and zeroth-order Michaelis-Menten kinetics could be used for the prediction of the kinetic constants.

Ratio of Diffusion Coefficient to Mobility for Electrons in SF6-Air and Freon-Nitrogen Mixtures

The ratio of diffusion coefficient to mobility (D/¿) for electrons has been measured in SF6-air and freon-nitrogen mixtures for various concentrations of SF6 and freon in the mixtures over the range 140¿ E/p¿ 220 V.cm-1 - torr-1. In SF6-air mixtures, the values of D/¿ were always observed to lie intermediate between the values for the pure gases. However, in freon-nitrogen mixtures, with a small concentration (10 percent) of freon in the mixture, the values of D/¿ are found to lie above the boundaries determined by the pure gases. In this mixture, over the lower E/p range (140 to 190) the electrons appear to lose a large fraction of their energy by the excitation of the complex freon molecules, while at higher E/p values (200 to 240), the excitation and consequent deexcitation of nitrogen molecules and its metastables seem to cause an increased rate of ionization of freon molecules.

A model for doped-oxide-source diffusion with a chemical reaction at the silicon-silicon dioxide interface

A mathematical model for doped-oxide-source diffusion is proposed. In this model the concept of segregation of impurity at the silicon-silicon dioxide is used and also a constant of “rate limitation” is introduced through a chemical reaction at the interface.

Strontium diffusion in feldspars—a laboratory study

Sr90 Radiotracer diffusion studies have been carried out on crystals of orthoclase and microcline using an ion implantation method. The activation energies are consistent with calculations based on mineral age data.

Diffusion of localized optical excitations and trap emission in ruby

Using the critical percolation conductance method the energy-dependent diffusion coefficient associated with thermally assisted transfer of the R1 line excitation between single Cr3+ ions with strain-induced randomness has been calculated in the 4A2 to E(2E) transition energies. For localized states sufficiently far away from the mobility edge the energy transfer is dominated by dipolar interactions, while very close to the mobility edge it is determined by short-range exchange interactions. Using the above energy-dependent diffusion coefficient a macroscopic diffusion equation is solved for the rate of light emission by Cr3+ ion-pair traps to which single-ion excitations are transferred. The dipolar mechanism leads to good agreement with recent measurements of the pair emission rate by Koo et al. (Phys. Rev. Lett., vol.35, p.1669 (1975)) right up to the mobility edge.

A comparative molecular dynamics study of diffusion of n-decane and 3-methyl pentane in Y zeolite

Molecular dynamics simulations are reported on the structure and dynamics of n-decane and 3-methylpentane in zeolite NaY. We have calculated several properties such as the center of mass-center of mass rdf, the end-end distance distribution, bond angle distribution and dihedral angle distribution. We have also analysed trajectory to obtain diffusivity and velocity autocorrelation function (VACF). Surprisingly, the diffusivity of 3-methylpentane which is having larger cross-section perpendicular to the long molecular axis is higher than n-decane at 300 K. Activation energies have been obtained from simulations performed at 200 K, 300 K, 350 K, 400 K and 450 K in the NVE ensemble. These results can be understood in terms of the previously known levitation effect. Arrhenious plot has higher value of slope for n-decane (5 center dot 9 kJ/mol) than 3-methylpentane (3 center dot 7 kJ/mol) in agreement with the prediction of levitation effect.

Diffusion and Creep in Silica-Doped Tetragonal Zirconia

Silica segregation at two grain junctions or in amorphous triple junction pockets can influence creep by altering the grain-boundary diffusion coefficient. Although the addition of silica to superplastic yttria-stabilized tetragonal zirconia enhances ductility, differences in reported creep parameters have limited critical identification of rate controlling mechanisms. The present study on a pure 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) and 3YTZ with 0.39 or 3.9 wt% silica involved a detailed characterization of creep over a wide range of experimental conditions and also tracer diffusion measurements. The data broadly show transitions in creep stress exponents from n∼1 to ∼2 to ∼3 with a decrease in the stress. The data at high stresses are consistent with Coble diffusion creep, and creep at lower stresses is attributed to interface-controlled diffusion creep. Measurements indicated that silica does not have any significant influence on grain boundary or lattice diffusion, and this is consistent with the observation that 3YTZ and 3YTZ with 0.39% or 3.9% silica exhibit essentially identical creep behavior in the Coble creep regime. Silica influences the interface control process so that the transitions in stress exponents are pushed to lower stresses with an increase in silica content.

Topological close packed mu phase formation and the determination of diffusion parameters in the Co-Mo system

The study on the formation and growth of topological close packed (TCP) compounds is important to understand the performance of turbine blades in jet engine applications. These deleterious phases grow mainly by diffusion process in the superalloy substrate. Significant volume change was found because of growth of the p phase in Co-Mo system. Growth kinetics of this phase and different diffusion parameters, like interdiffusion, intrinsic and tracer diffusion coefficients are calculated. Further the activation energy, which provides an idea about the mechanism, is determined. Moreover, the interdiffusion coefficient in Co(Mo) solid solution and impurity diffusion coefficient of Mo in Co are determined.

Anomalous reaction-diffusion as a model of nonexponential DNA escape kinetics

We show that data from recent experiments carried out on the kinetics of DNA escape from alpha-hemolysin nanopores [M. Wiggin, C. Tropini, C. T. Cossa, N. N. Jetha, and A. Marziali, Biophys. J. 95, 5317 (2008)] may be rationalized by a model of chain dynamics based on the anomalous diffusion of a particle moving in a harmonic well in the presence of a delta function sink. The experiments of Wiggin found, among other things, that the occasional occurrence of unusually long escape times in the distribution of chain trapping events led to nonexponential decays in the survival probability, S(t), of the DNA molecules within the nanopore. Wiggin ascribed this nonexponentiality to the existence of a distribution of trapping potentials, which they suggested was theresult of stochastic interactions between the bases of the DNA and the amino acids located on the surface of the nanopore. Based on this idea, they showed that the experimentally determined S(t) could be well fit in both the short and long time regimes by a function of the form (1+t/tau)(-alpha) (the so called Becquerel function). In our model, S(t) is found to be given by a Mittag-Leffler function at short times and by a generalized Mittag-Leffler function at long times. By suitable choice of certain parameter values, these functions are found to fit the experimental S(t) even better than the Becquerel function. Anomalous diffusion of DNA within the trap prior to escape over a barrier of fixed height may therefore provide a second, plausible explanation of the data, and may offer fresh perspectives on similar trapping and escape problems.

Diffusion of flexible, charged, nanoscopic molecules in solution: Size and pH dependence for PAMAM dendrimer

In order to understand self-diffusion (D) of a charged, flexible, and porous nanoscopic molecule in water, we carry out very long, fully atomistic molecular dynamics simulation of PAMAM dendrimer up to eight generations in explicit salt water under varying pH. We find that while the radius of gyration (R-g) varies as N-1/3, the self-diffusion constant (D) scales, surprisingly, as N-alpha, with alpha=0.39 at high pH and 0.5 at neutral pH, indicating a dramatic breakdown of Stokes-Einstein relation for diffusion of charged nanoscopic molecules. The variation in D as a function of radius of gyration demonstrates the importance of treating water and ions explicitly in the diffusion process of a flexible nanoscopic molecule. In agreement with recent experiments, the self-diffusion constant increases with pH, revealing the importance of dielectric friction in the diffusion process. The shape of a dendrimer is found to fluctuate on a nanosecond time scale. We argue that this flexibility (and also the porosity) of the dendrimer may play an important role in determining the mean square displacement of the dendrimer and the breakdown of the Stokes-Einstein relation between diffusion constant and the radius.