Rotational and translational self-diffusion in concentrated suspensions of permeable particles

In our recent work on concentrated suspensions of uniformly porous colloidal spheres with excluded volume interactions, a variety of short-time dynamic properties were calculated, except for the rotational self-diffusion coefficient. This missing quantity is included in the present paper. Using a precise hydrodynamic force multipole simulation method, the rotational self-diffusion coefficient is evaluated for concentrated suspensions of permeable particles. Results are presented for particle volume fractions up to 45%, and for a wide range of permeability values. From the simulation results and earlier results for the first-order virial coefficient, we find that the rotational self-diffusion coefficient of permeable spheres can be scaled to the corresponding coefficient of impermeable particles of the same size. We also show that a similar scaling applies to the translational self-diffusion coefficient considered earlier. From the scaling relations, accurate analytic approximations for the rotational and translational self-diffusion coefficients in concentrated systems are obtained, useful to the experimental analysis of permeable-particle diffusion. The simulation results for rotational diffusion of permeable particles are used to show that a generalized Stokes-Einstein-Debye relation between rotational self-diffusion coefficient and high-frequency viscosity is not satisfied.Comment: 4 figure

Self-diffusion of polymers in cartilage as studied by pulsed field gradient NMR

Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) was used to investigate the self-diffusion behaviour of polymers in cartilage. Polyethylene glycol and dextran with different molecular weights and in different concentrations were used as model compounds to mimic the diffusion behaviour of metabolites of cartilage. The polymer self-diffusion depends extremely on the observation time: The short-time self-diffusion coefficients (diffusion time Delta approximately 15 ms) are subjected to a rather non-specific obstruction effect that depends mainly on the molecular weights of the applied polymers as well as on the water content of the cartilage. The observed self-diffusion coefficients decrease with increasing molecular weights of the polymers and with a decreasing water content of the cartilage. In contrast, the long-time self-diffusion coefficients of the polymers in cartilage (diffusion time Delta approximately 600 ms) reflect the structural properties of the tissue. Measurements at different water contents, different molecular weights of the polymers and varying observation times suggest that primarily the collagenous network of cartilage but also the entanglements of the polymer chains themselves are responsible for the observed restricted diffusion. Additionally, anomalous restricted diffusion was shown to occur already in concentrated polymer solutions

Self-diffusion in sheared suspensions

Self-diffusion in a suspension of spherical particles in steady linear shear flow is investigated by following the time evolution of the correlation of number density fluctuations. Expressions are presented for the evaluation of the self-diffusivity in a suspension which is either raacroscopically quiescent or in linear flow at arbitrary Peclet number Pe = ẏa^2/2D, where ẏ is the shear rate, a is the particle radius, and D = k_BT/6πηa is the diffusion coefficient of an isolated particle. Here, k_B is Boltzmann's constant, T is the absolute temperature, and η is the viscosity of the suspending fluid. The short-time self-diffusion tensor is given by k_BT times the microstructural average of the hydrodynamic mobility of a particle, and depends on the volume fraction ø = 4/3πa^3n and Pe only when hydrodynamic interactions are considered. As a tagged particle moves through the suspension, it perturbs the average microstructure, and the long-time self-diffusion tensor, D_∞^s, is given by the sum of D_0^s and the correlation of the flux of a tagged particle with this perturbation. In a flowing suspension both D_0^s and D_∞^s are anisotropic, in general, with the anisotropy of D_0^s due solely to that of the steady microstructure. The influence of flow upon D_∞^s is more involved, having three parts: the first is due to the non-equilibrium microstructure, the second is due to the perturbation to the microstructure caused by the motion of a tagged particle, and the third is by providing a mechanism for diffusion that is absent in a quiescent suspension through correlation of hydrodynamic velocity fluctuations. The self-diffusivity in a simply sheared suspension of identical hard spheres is determined to O(φPe^(3/2)) for Pe « 1 and ø « 1, both with and without hydro-dynamic interactions between the particles. The leading dependence upon flow of D_0^s is 0.22DøPeÊ, where Ê is the rate-of-strain tensor made dimensionless with ẏ. Regardless of whether or not the particles interact hydrodynamically, flow influences D_∞^s at O(øPe) and O(øPe^(3/2)). In the absence of hydrodynamics, the leading correction is proportional to øPeDÊ. The correction of O(øPe^(3/2)), which results from a singular advection-diffusion problem, is proportional, in the absence of hydrodynamic interactions, to øPe^(3/2)DI; when hydrodynamics are included, the correction is given by two terms, one proportional to Ê, and the second a non-isotropic tensor. At high ø a scaling theory based on the approach of Brady (1994) is used to approximate D_∞^s. For weak flows the long-time self-diffusivity factors into the product of the long-time self-diffusivity in the absence of flow and a non-dimensional function of Pe = ẏa^2/2D^s_0(φ)$. At small Pe the dependence on Pe is the same as at low ø

Self-diffusion in granular gases

The coefficient of self-diffusion for a homogeneously cooling granular gas changes significantly if the impact-velocity dependence of the restitution coefficient $\epsilon$ is taken into account. For the case of a constant $\epsilon$ the particles spread logarithmically slow with time, whereas the velocity dependent coefficient yields a power law time-dependence. The impact of the difference in these time dependences on the properties of a freely cooling granular gas is discussed.Comment: 6 pages, no figure

Self-diffusion in granular gases: Green-Kubo versus Chapman-Enskog

We study the diffusion of tracers (self-diffusion) in a homogeneously cooling gas of dissipative particles, using the Green-Kubo relation and the Chapman-Enskog approach. The dissipative particle collisions are described by the coefficient of restitution $\epsilon$ which for realistic material properties depends on the impact velocity. First, we consider self-diffusion using a constant coefficient of restitution, $\epsilon=$const, as frequently used to simplify the analysis. Second, self-diffusion is studied for a simplified (stepwise) dependence of $\epsilon$ on the impact velocity. Finally, diffusion is considered for gases of realistic viscoelastic particles. We find that for $\epsilon=$const both methods lead to the same result for the self-diffusion coefficient. For the case of impact-velocity dependent coefficients of restitution, the Green-Kubo method is, however, either restrictive or too complicated for practical application, therefore we compute the diffusion coefficient using the Chapman-Enskog method. We conclude that in application to granular gases, the Chapman-Enskog approach is preferable for deriving kinetic coefficients.Comment: 15 pages, 1 figur

Precise Control of Molecular Self-Diffusion in Isoreticular and Multivariate Metal-Organic Frameworks.

Understanding the factors that affect self-diffusion in isoreticular and multivariate (MTV) MOFs is key to their application in drug delivery, separations, and heterogeneous catalysis. Here, we measure the apparent self-diffusion of solvents saturated within the pores of large single crystals of MOF-5, IRMOF-3 (amino-functionalized MOF-5), and 17 MTV-MOF-5/IRMOF-3 materials at various mole fractions. We find that the apparent self-diffusion coefficient of N,N-dimethylformamide (DMF) may be tuned linearly between the diffusion coefficients of MOF-5 and IRMOF-3 as a function of the linker mole fraction. We compare a series of solvents at saturation in MOF-5 and IRMOF-3 to elucidate the mechanism by which the linker amino groups tune molecular diffusion. The ratio of the self-diffusion coefficients for solvents in MOF-5 to those in IRMOF-3 is similar across all solvents tested, regardless of solvent polarity. We conclude that average pore aperture, not solvent-linker chemical interactions, is the primary factor responsible for the different diffusion dynamics upon introduction of an amino group to the linker

Self-diffusion in sheared colloidal suspensions: violation of fluctuation-dissipation relation

Using memory-function formalism we show that in sheared colloidal suspensions the fluctuation-dissipation theorem for self-diffusion, i.e. Einstein's relation between self-diffusion and mobility tensors, is violated and propose a new way to measure this violation in Brownian Dynamics simulations. We derive mode-coupling expressions for the tagged particle friction tensor and for an effective, shear-rate dependent temperature

Self-diffusion coefficient of the square-well fluid from molecular dynamics within the constant force approach

We present a systematic study of the self-diffusion coefficient for a fluid of particles interacting via the square-well pair potential by means of molecular dynamics simulations in the canonical (N,V,T) ensemble. The discrete nature of the interaction potential is modeled through the constant force approximation and the self-diffusion coefficients is determined for several packing fractions at super critical thermodynamic states. The dependence of the self-diffusion coefficient with the potential range $\lambda$ is analyzed in the range of $1.1 \leq \lambda \leq 1.5$. The obtained molecular dynamics simulations results are in agreement with the self-diffusion coefficient predicted with the Enskog method. Additionally, we soh that the diffusion coefficient is very sensitive to the potential range, $\lambda$, at low densities leading to a density dependence of this coefficient not shared with other macroscopic properties such as the equation of state. The constant force approximation used in this work to model the discrete pair potential has shown to be an excellent scheme to compute the transport properties using standar computer simulations. Finally, the simulation results presented here are resourceful to improving theoretical approaches, such as the Enskog method

Theory of self-diffusion in GaAs

Ab initio molecular dynamics simulations are employed to investigate the dominant migration mechanism of the gallium vacancy in gaas as well as to assess its free energy of formation and the rate constant of gallium self-diffusion. our analysis suggests that the vacancy migrates by second nearest neighbour hops. the calculated self-diffusion constant is in good agreement with the experimental value obtained in ^69 GaAs/ ^71 GaAs isotope heterostructures and at significant variance with that obtained earlier from interdiffusion experiments in GaAlAs/GaAs-heterostructures.Comment: 15 pages, 4 figures. Z. Phys. Chem, in prin

A Nonlinear Splitting Algorithm for Systems of Partial Differential Equations with self-Diffusion

Systems of reaction-diffusion equations are commonly used in biological models of food chains. The populations and their complicated interactions present numerous challenges in theory and in numerical approximation. In particular, self-diffusion is a nonlinear term that models overcrowding of a particular species. The nonlinearity complicates attempts to construct efficient and accurate numerical approximations of the underlying systems of equations. In this paper, a new nonlinear splitting algorithm is designed for a partial differential equation that incorporates self-diffusion. We present a general model that incorporates self-diffusion and develop a numerical approximation. The numerical analysis of the approximation provides criteria for stability and convergence. Numerical examples are used to illustrate the theoretical results