Percolation perspective on sites not visited by a random walk in two dimensions.

We consider the percolation problem of sites on an L×L square lattice with periodic boundary conditions which were unvisited by a random walk of N=uL^{2} steps, i.e., are vacant. Most of the results are obtained from numerical simulations. Unlike its higher-dimensional counterparts, this problem has no sharp percolation threshold and the spanning (percolation) probability is a smooth function monotonically decreasing with u. The clusters of vacant sites are not fractal but have fractal boundaries of dimension 4/3. The lattice size L is the only large length scale in this problem. The typical mass (number of sites s) in the largest cluster is proportional to L^{2}, and the mean mass of the remaining (smaller) clusters is also proportional to L^{2}. The normalized (per site) density n_{s} of clusters of size (mass) s is proportional to s^{-τ}, while the volume fraction P_{k} occupied by the kth largest cluster scales as k^{-q}. We put forward a heuristic argument that τ=2 and q=1. However, the numerically measured values are τ≈1.83 and q≈1.20. We suggest that these are effective exponents that drift towards their asymptotic values with increasing L as slowly as 1/lnL approaches zero.

Percolation of sites not removed by a random walker in d dimensions.

How does removal of sites by a random walk lead to blockage of percolation? To study this problem of correlated site percolation, we consider a random walk (RW) of N=uL^{d} steps on a d-dimensional hypercubic lattice of size L^{d} (with periodic boundaries). We systematically explore dependence of the probability Π_{d}(L,u) of percolation (existence of a spanning cluster) of sites not removed by the RW on L and u. The concentration of unvisited sites decays exponentially with increasing u, while the visited sites are highly correlated-their correlations decaying with the distance r as 1/r^{d-2} (in d>2). On increasing L, the percolation probability Π_{d}(L,u) approaches a step function, jumping from 1 to 0 when u crosses a percolation threshold u_{c} that is close to 3 for all 3≤d≤6. Within numerical accuracy, the correlation length associated with percolation diverges with exponents consistent with ν=2/(d-2). There is no percolation threshold at the lower critical dimension of d=2, with the percolation probability approaching a smooth function Π_{2}(∞,u)>0.

Localization of random walks to competing manifolds of distinct dimensions.

We consider localization of a random walk (RW) when attracted or repelled by multiple extended manifolds of different dimensionalities. In particular, we consider a RW near a rectangular wedge in two dimensions, where the (zero-dimensional) corner and the (one-dimensional) wall have competing localization properties. This model applies also (as cross section) to an ideal polymer attracted to the surface or edge of a rectangular wedge in three dimensions. More generally, we consider (d-1)- and (d-2)-dimensional manifolds in d-dimensional space, where attractive interactions are (fully or marginally) relevant. The RW can then be in one of four phases where it is localized to neither, one, or both manifolds. The four phases merge at a special multicritical point where (away from the manifolds) the RW spreads diffusively. Extensive numerical analyses on two-dimensional RWs confined inside or outside a rectangular wedge confirm general features expected from a continuum theory, but also exhibit unexpected attributes, such as a reentrant localization to the corner while repelled by it.

Nonequilibrium interactions between ideal polymers and a repulsive surface.

We use Newtonian and overdamped Langevin dynamics to study long flexible polymers dragged by an external force at a constant velocity v. The work W performed by that force depends on the initial state of the polymer and the details of the process. The Jarzynski equality can be used to relate the nonequilibrium work distribution P(W) obtained from repeated experiments to the equilibrium free energy difference ΔF between the initial and final states. We use the power law dependence of the geometrical and dynamical characteristics of the polymer on the number of monomers N to suggest the existence of a critical velocity v_{c}(N), such that for v

Attractive and repulsive polymer-mediated forces between scale-free surfaces.

We consider forces acting on objects immersed in, or attached to, long fluctuating polymers. The confinement of the polymer by the obstacles results in polymer-mediated forces that can be repulsive (due to loss of entropy) or attractive (if some or all surfaces are covered by adsorbing layers). The strength and sign of the force in general depends on the detailed shape and adsorption properties of the obstacles but assumes simple universal forms if characteristic length scales associated with the objects are large. This occurs for scale-free shapes (such as a flat plate, straight wire, or cone) when the polymer is repelled by the obstacles or is marginally attracted to it (close to the depinning transition where the absorption length is infinite). In such cases, the separation h between obstacles is the only relevant macroscopic length scale, and the polymer-mediated force equals Ak_{B}T/h, where T is temperature. The amplitude A is akin to a critical exponent, depending only on geometry and universality of the polymer system. The value of A, which we compute for simple geometries and ideal polymers, can be positive or negative. Remarkably, we find A=0 for ideal polymers at the adsorption transition point, irrespective of shapes of the obstacles, i.e., at this special point there is no polymer-mediated force between obstacles (scale free or not).

Pinning and unbinding of ideal polymers from a wedge corner.

A polymer repelled by unfavorable interactions with a uniform flat surface may still be pinned to attractive edges and corners. This is demonstrated by considering adsorption of a two-dimensional ideal polymer to an attractive corner of a repulsive wedge. The well-known mapping between the statistical mechanics of an ideal polymer and the quantum problem of a particle in a potential is then used to analyze the singular behavior of the unbinding transition of the polymer. The divergence of the localization length is found to be governed by an exponent that varies continuously with the angle (when reflex). Numerical treatment of the discrete (lattice) version of such an adsorption problem confirms this behavior.

Winding angles of long lattice walks.

We study the winding angles of random and self-avoiding walks (SAWs) on square and cubic lattices with number of steps N ranging up to 10(7). We show that the mean square winding angle 〈θ(2)〉 of random walks converges to the theoretical form when N → ∞. For self-avoiding walks on the square lattice, we show that the ratio 〈θ(4)〉/〈θ(2)〉(2) converges slowly to the Gaussian value 3. For self-avoiding walks on the cubic lattice, we find that the ratio 〈θ(4)〉/〈θ(2)〉(2) exhibits non-monotonic dependence on N and reaches a maximum of 3.73(1) for N ≈ 10(4). We show that to a good approximation, the square winding angle of a self-avoiding walk on the cubic lattice can be obtained from the summation of the square change in the winding angles of lnN independent segments of the walk, where the ith segment contains 2(i) steps. We find that the square winding angle of the ith segment increases approximately as i(0.5), which leads to an increase of the total square winding angle proportional to (lnN)(1.5).

Diffusion in the presence of scale-free absorbing boundaries.

Scale-free surfaces, such as cones, remain unchanged under a simultaneous expansion of all coordinates by the same factor. Probability density of a particle diffusing near such absorbing surface at large time approaches a simple form that incorporates power-law dependencies on time and distance from a special point, such as apex of the cone, which are characterized by a single exponent η. The same exponent is used to describe the number of spatial conformations of long ideal polymer attached to the special point of a repulsive surface of the same geometry and can be used in calculation of entropic forces between such polymers and surfaces. We use the solution of diffusion equation near such surfaces to find the numerical values of η, as well as to provide some insight into the behavior of ideal polymers near such surfaces.

Long polymers near wedges and cones.

We perform a Monte Carlo study of N-step self-avoiding walks, attached to the corner of an impenetrable wedge in two dimensions (d=2), or the tip of an impenetrable cone in d=3, of sizes ranging up to N=10(6) steps. We find that the critical exponent γ(α), which determines the dependence of the number of available conformations on N for a cone or wedge with opening angle α, is in good agreement with the theory for d=2. We study the end-point distribution of the walks in the allowed space and find similarities to the known behavior of random walks (ideal polymers) in the same geometry. For example, the ratio between the mean square end-to-end distances of a polymer near the cone or wedge and a polymer in free space depends linearly on γ(α), as is known for ideal polymers. We show that the end-point distribution of polymers attached to a wedge does not separate into a product of angular and radial functions, as it does for ideal polymers in the same geometry. The angular dependence of the end position of polymers near the wedge differs from theoretical predictions.

Entropic pressure in lattice models for polymers.

In lattice models, local pressure on a surface is derived from the change in the free energy of the system due to the exclusion of a certain boundary site, while the total force on the surface can be obtained by a similar exclusion of all surface sites. In these definitions, while the total force on the surface of a lattice system matches the force measured in a continuous system, the local pressure does not. Moreover, in a lattice system, the sum of the local pressures is not equal to the total force as is required in a continuous system. The difference is caused by correlation between occupations of surface sites as well as finite displacement of surface elements used in the definition of the pressures and the force. This problem is particularly acute in the studies of entropic pressure of polymers represented by random or self-avoiding walks on a lattice. We propose a modified expression for the local pressure which satisfies the proper relation between the pressure and the total force, and show that for a single ideal polymer in the presence of scale-invariant boundaries it produces quantitatively correct values for continuous systems. The required correction to the pressure is non-local, i.e., it depends on long range correlations between contact points of the polymer and the surface.

Ideal polymers near scale-free surfaces.

The number of allowed configurations of a polymer is reduced by the presence of a repulsive surface resulting in an entropic force between them. We develop a method to calculate the entropic force, and detailed pressure distribution, for long ideal polymers near a scale-free repulsive surface. For infinite polymers the monomer density is related to the electrostatic potential near a conducting surface of a charge placed at the point where the polymer end is held. Pressure of the polymer on the surface is then related to the charge density distribution in the electrostatic problem. We derive explicit expressions for pressure distributions and monomer densities for ideal polymers near a two- or three-dimensional wedge, and for a circular cone in three dimensions. Pressure of the polymer diverges near sharp corners in a manner resembling (but not identical to) the electric field divergence near conducting surfaces. We provide formalism for calculation of all components of the total force in situations without axial symmetry.

Polymer-mediated entropic forces between scale-free objects.

The number of configurations of a polymer is reduced in the presence of a barrier or an obstacle. The resulting loss of entropy adds a repulsive component to other forces generated by interaction potentials. When the obstructions are scale invariant shapes (such as cones, wedges, lines, or planes) the only relevant length scales are the polymer size R(0) and characteristic separations, severely constraining the functional form of entropic forces. Specifically, we consider a polymer (single strand or star) attached to the tip of a cone, at a separation h from a surface (or another cone). At close proximity, such that h << R(0), separation is the only remaining relevant scale and the entropic force must take the form F = Ak(B)T/h. The amplitude A is universal and can be related to exponents η governing the anomalous scaling of polymer correlations in the presence of obstacles. We use analytical, numerical, and ε-expansion techniques to compute the exponent η for a polymer attached to the tip of the cone (with or without an additional plate or cone) for ideal and self-avoiding polymers. The entropic force is of the order of 0.1 pN at 0.1 µm for a single polymer and can be increased for a star polymer.

First-passage distributions in a collective model of anomalous diffusion with tunable exponent.

We consider a model system in which anomalous diffusion is generated by superposition of underlying linear modes with a broad range of relaxation times. In the language of Gaussian polymers, our model corresponds to Rouse (Fourier) modes whose friction coefficients scale as wave number to the power 2-z. A single (tagged) monomer then executes subdiffusion over a broad range of time scales, and its mean square displacement increases as t(alpha) with alpha = 1/z. To demonstrate nontrivial aspects of the model, we numerically study the absorption of the tagged particle in one dimension near an absorbing boundary or in the interval between two such boundaries. We obtain absorption probability densities as a function of time, as well as the position-dependent distribution for unabsorbed particles, at several values of alpha. Each of these properties has features characterized by exponents that depend on alpha. Characteristic distributions found for different values of alpha have similar qualitative features, but are not simply related quantitatively. Comparison of the motion of translocation coordinate of a polymer moving through a pore in a membrane with the diffusing tagged monomer with identical alpha also reveals quantitative differences.

Structure and dynamics of vibrated granular chains: comparison to equilibrium polymers.

We show that the statistical properties of a vibrated granular bead chain are similar to standard models of polymers in equilibrium. Granular chains of length up to N=1024 beads were confined within a circular vibrating bed, and their configurations were imaged. To differentiate the effects of persistence and confinement on the chain, we compared with simulations of both persistent random-walk (RW) and self-avoiding walk (SAW) models. Static properties, such as the radius of gyration and structure factor, are governed for short chains (N

One-dimensional gas of hard needles.

We study a one-dimensional gas of needlelike objects as a testing ground for a formalism that relates the thermodynamic properties of "hard" potentials to the probabilities for contacts between particles. Specifically, we use Monte Carlo methods to calculate the pressure and elasticity coefficient of the hard-needle gas as a function of its density. The results are then compared to the same quantities obtained analytically from a transfer-matrix approach.

Probability distributions for polymer translocation.

We study the passage (translocation) of a self-avoiding polymer through a membrane pore in two dimensions. In particular, we numerically measure the probability distribution Q(T) of the translocation time T, and the distribution P(s,t) of the translocation coordinate s at various times t. When scaled with the mean translocation time T , Q(T) becomes independent of polymer length, and decays exponentially for large T. The probability P(s,t) is well described by a Gaussian at short times, with a variance of s that grows subdiffusively as talpha with alpha approximately 0.8. For times exceeding T , P(s,t) of the polymers that have not yet finished their translocation has a nontrivial stable shape.

Anomalous diffusion with absorbing boundary.

In a very long Gaussian polymer on time scales shorter than the maximal relaxation time, the mean squared distance traveled by a tagged monomer grows as approximately t(1/2) . We analyze such subdiffusive behavior in the presence of one or two absorbing boundaries and demonstrate the differences between this process and the subdiffusion described by the fractional Fokker-Planck equation. In particular, we show that the mean absorption time of diffuser between two absorbing boundaries is finite. Our results restrict the form of the effective dispersion equation that may describe such subdiffusive processes.

Elasticity of a system with noncentral potentials.

We derive expressions for determination of the stress and the elastic constants in systems composed of particles interacting via noncentral two-body potentials as thermal averages of products of first and second partial derivatives of the interparticle potentials and components of the interparticle separation vectors. These results are adapted to hard potentials, where the stress and the elastic constants are expressed as thermal averages of the components of normals to contact surfaces between the particles and components of vectors separating their centers. The averages require knowledge of the simultaneous contact probabilities of two pairs of particles. We apply the expressions to particles for which a contact function can be defined, and demonstrate the feasibility of the method by computing the stress and the elastic constants of a two-dimensional system of hard ellipses using Monte Carlo simulations.

Knots in globule and coil phases of a model polyethylene.

We examine the statistics of knots with numerical simulations of a simplified model of polyethylene. We can simulate polymers of up to 1000 monomers (each representing roughly three CH(2) groups), at a range of temperatures spanning coil (good solvent) and globule (bad solvent) phases. We quantify the abundance of knots in the globule phase and in confined polymers, and their rarity in the swollen phase. Since our polymers are open, we consider (and test) various operational definitions for knots, which are rigorously defined only for closed chains. We also associate a typical size with individual knots, which are found to be small (tight and localized) in the swollen phase but large (loose and spread out) in the dense phases.

Apex exponents for polymer-probe interactions.

We consider self-avoiding polymers attached to the tip of an impenetrable probe. The scaling exponents gamma(1) and gamma(2), characterizing the number of configurations for the attachment of the polymer by one end, or at its midpoint, vary continuously with the tip's angle. These apex exponents are calculated analytically by epsilon expansion, and numerically by simulations in three dimensions. We find that when the polymer can move through the attachment point, it typically slides to one end; the apex exponents quantify the entropic barrier to threading the eye of the probe.