Anomalous aggregation regimes of temperature-dependent Smoluchowski equations.

Temperature-dependent Smoluchowski equations describe the ballistic agglomeration. In contrast to the standard Smoluchowski equations for the evolution of cluster densities, with constant rate coefficients, the temperature-dependent equations describe both-the evolution of the densities as well as cluster temperatures, which determine the agglomeration rates. To solve these equations, we develop a Monte Carlo technique based on the low-rank approximation for the aggregation kernel. Using this highly effective approach, we perform a comprehensive study of the kinetic phase diagram of the system and reveal a few surprising regimes, including permanent temperature growth and "density separation" regime, with a large gap in the size distribution for middle-size clusters. We perform scaling analysis and classify the aggregation kernels for the temperature-dependent equations. Furthermore, we conjecture the lack of gelation in such systems. The results of the scaling theory agree well with the simulation data.

Role of energy in ballistic agglomeration.

We study a ballistic agglomeration process in the reaction-controlled limit. Cluster densities obey an infinite set of Smoluchowski rate equations, with rates dependent on the average particle energy. The latter is the same for all cluster species in the reaction-controlled limit and obeys an equation depending on densities. We express the average energy through the total cluster density that allows us to reduce the governing equations to the standard Smoluchowski equations. We derive basic asymptotic behaviors and verify them numerically. We also apply our formalism to the agglomeration of dark matter.

Steady oscillations in aggregation-fragmentation processes.

We report surprising steady oscillations in aggregation-fragmentation processes. Oscillating solutions are observed for the class of aggregation kernels K_{i,j}=i^{ν}j^{µ}+j^{ν}i^{µ} homogeneous in masses i and j of merging clusters and fragmentation kernels, F_{ij}=λK_{ij}, with parameter λ quantifying the intensity of the disruptive impacts. We assume a complete decomposition (shattering) of colliding partners into monomers. We show that an assumption of a steady-state distribution of cluster sizes, compatible with governing equations, yields a power law with an exponential cutoff. This prediction agrees with simulation results when θ≡ν-µ<1. For θ=ν-µ>1, however, the densities exhibit an oscillatory behavior. While these oscillations decay for not very small λ, they become steady if θ is close to 2 and λ is very small. Simulation results lead to a conjecture that for θ<1 the system has a stable fixed point, corresponding to the steady-state density distribution, while for any θ>1 there exists a critical value λ_{c}, such that for λ<λ_{c}, the system has an attracting limit cycle. This is rather striking for a closed system of Smoluchowski-like equations, lacking any sinks and sources of mass.

Theoretical and numerical analysis of nano-actuators based on grafted polyelectrolytes in an electric field.

We analyze, theoretically and by means of molecular dynamics (MD) simulations, the generation of mechanical force by a polyelectrolyte (PE) chain grafted to a plane and exposed to an external electric field; the free end of the chain is linked to a deformable target body. Varying the field, one can alter the length of the non-adsorbed (bulk) part of the chain and hence the deformation of the target body and the arising force. We focus on the impact of added salt on the magnitude of the generated force, which is especially important for applications. In particular, we develop a simple variational theory for the double layer formed near electrodes to compute the electric field acting on the bulk part of the chain. Our theoretical predictions agree well with the MD simulations. Next, we study the effectiveness of possible PE-based nano-vices, comprised of two clenching planes connected by PEs exposed to an external electric field. We analyze a novel phenomenon - two-dimensional diffusion of a nano-particle, clenched between two planes, and introduce a quantitative criterion for clenching efficiency, the clenching coefficient. It is defined as a logarithm of the ratio of the diffusion coefficients of a free and clenched particle. Using first a microscopic counterpart of the Coulomb friction model, and then a novel microscopic model based on surface phonons, with the vibration direction normal to the surface, we calculate the clenching coefficient as a function of the external electric field. Our results demonstrate a dramatic decrease of the diffusion coefficient of a clenched nano-particle for the range of parameters relevant for applications; this proves the effectiveness of the PE-based nano-vices.

Phase transitions in systems with aggregation and shattering.

We consider a system of clusters made of elementary building blocks, monomers, and evolving via collisions between diffusing monomers and immobile composite clusters. In our model, the cluster-monomer collision can lead to the attachment of the monomer to the cluster (addition process) or to the total breakup of the cluster (shattering process). A phase transition, separating qualitatively different behaviors, occurs when the probability of shattering events exceeds a certain threshold. The novel feature of the phase transition is the dramatic dependence on the initial conditions.

Oscillations in Aggregation-Shattering Processes.

We observe never-ending oscillations in systems undergoing collision-controlled aggregation and shattering. Specifically, we investigate aggregation-shattering processes with aggregation kernels K_{i,j}=(i/j)^{a}+(j/i)^{a} and shattering kernels F_{i,j}=λK_{i,j}, where i and j are cluster sizes, and parameter λ quantifies the strength of shattering. When 0≤a<1/2, there are no oscillations, and the system monotonically approaches a steady state for all values of λ; in this region, we obtain an analytical solution for the stationary cluster size distribution. Numerical solutions of the rate equations show that oscillations emerge in the 1/2

Generation of mechanical force by grafted polyelectrolytes in an electric field: application to polyelectrolyte-based nano-devices.

We analyse theoretically and by means of molecular dynamics (MD) simulations the generation of mechanical force by a polyelectrolyte (PE) chain grafted to a plane. The PE is exposed to an external electric field that favours its adsorption on the plane. The free end of the chain is linked to a deformable target body. By varying the field, one can alter the length of the non-adsorbed part of the chain. This entails variation of the deformation of the target body and hence variation of the force arising in the body. Our theoretical predictions for the generated force are in very good agreement with the MD data. Using the theory developed for the generated force, we study the effectiveness of possible PE-based nano-vices, composed of two clenching planes connected by PEs and exposed to an external electric field. We exploit the Cundall-Strack solid friction model to describe the friction between a particle and the clenching planes. We compute the diffusion coefficient of a clenched particle and show that it drastically decreases even in weak applied fields. This demonstrates the efficacy of the PE-based nano-vices, which may be a possible alternative to the existing nanotube nano-tweezers and optical tweezers.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

Generation of mechanical force by grafted polyelectrolytes in an electric field.

We study theoretically and by means of molecular dynamics (MD) simulations the generation of mechanical force by grafted polyelectrolytes in an external electric field, which favors its adsorption on the grafting plane. The force arises in deformable bodies linked to the free end of the chain. Varying the field, one controls the length of the nonadsorbed part of the chain and hence the deformation of the target body, i.e., the arising force too. We consider target bodies with a linear force-deformation relation and with a Hertzian one. While the first relation models a coiled Gaussian chain, the second one describes the force response of a squeezed colloidal particle. The theoretical dependences of generated force and compression of the target body on an applied field agree very well with the results of MD simulations. The analyzed phenomenon may play an important role in future nanomachinery, e.g., it may be used to design nanovices to fix nanosized objects.

Non-Fickian diffusion and the accumulation of methane bubbles in deep-water sediments.

In the absence of fractures, methane bubbles in deep-water sediments can be immovably trapped within a porous matrix by surface tension. The dominant mechanism of transfer of gas mass therefore becomes the diffusion of gas molecules through porewater. The accurate description of this process requires non-Fickian diffusion to be accounted for, including both thermal diffusion and gravitational action. We evaluate the diffusive flux of aqueous methane considering non-Fickian diffusion and predict the existence of extensive bubble mass accumulation zones within deep-water sediments. The limitation on the hydrate deposit capacity is revealed; too weak deposits cannot reach the base of the hydrate stability zone and form any bubbly horizon.

Surface-induced liquid-gas transition in salt-free solutions of model charged colloids.

We report a novel phenomenon of a surface-induced phase transition in salt-free solutions of charged colloids. We develop a theory of this effect and confirm it by Molecular Dynamics simulations. To describe the colloidal solution we apply a primitive model of electrolyte with a strong asymmetry of charge and size of the constituent particles - macroions and counterions. To quantify interactions of the colloidal particles with the neutral substrate we use a short-range potential which models dispersion van der Waals forces. These forces cause the attraction of colloids to the surface. We show that for high temperatures and weak attraction, only gradual increase of the macroion concentration in the near-surface layer is observed with increase of interaction strength. If however temperature drops below some threshold value, a new dense (liquid) phase is formed in the near-surface layer. It can be interpreted as a surface-induced first-order phase transition with a critical point. Using an appropriately adopted Maxwell construction, we find the binodal. Interestingly, the observed near-surface phase transition can occur at the absence of the bulk phase transition and may be seemingly classified as prewetting transition. The reported effect could be important for various technological applications where formation of colloidal particle layers with the desired properties is needed.

Translations and rotations are correlated in granular gases.

In a granular gas of rough particles the axis of rotation is shown to be correlated with the translational velocity of the particles. The average relative orientation of angular and linear velocities depends on the parameters which characterize the dissipative nature of the collision. We derive a simple theory for these correlations and validate it with numerical simulations for a wide range of coefficients of normal and tangential restitution. The limit of smooth spheres is shown to be singular: even an arbitrarily small roughness of the particles gives rise to orientational correlations.

Extremal collision sequences of particles on a line: optimal transmission of kinetic energy.

The transmission of kinetic energy through chains of inelastically colliding spheres is investigated for the case of constant coefficient of restitution epsilon=const and impact-velocity-dependent coefficient epsilon(v) for viscoelastic particles. We derive a theory for the optimal distribution of particle masses which maximize the energy transfer along the chain and check it numerically. We found that for epsilon=const, the mass distribution is a monotonous function which does not depend on the value of epsilon. In contrast, for epsilon(v) the mass distribution reveals a pronounced maximum, depending on the particle properties and on the chain length. The system investigated demonstrates that even for small and simple systems, the velocity dependence of the coefficient of restitution may lead to new effects with respect to the same systems under the simplifying approximation epsilon=const.

Coefficient of restitution of colliding viscoelastic spheres.

We perform a dimension analysis for colliding viscoelastic spheres to show that the coefficient of normal restitution epsilon depends on the impact velocity g as epsilon=1-gamma(1)g(1/5)+gamma(2)g(2/5)-/+..., in accordance with recent findings. We develop a simple theory to find explicit expressions for coefficients gamma(1) and gamma(2). Using these and few next expansion coefficients for epsilon(g) we construct a Padé approximation for this function which may be used for a wide range of impact velocities where the concept of the viscoelastic collision is valid. The obtained expression reproduces quite accurately the existing experimental dependence epsilon(g) for ice particles.