arXiv subjects

T. A. Vilgis

Publications and source records attributed to T. A. Vilgis.

At least 37 records · Page 2Linked to original sources

arXiv2008

Applications of a generalization of the nonlinear sigma model with O(d) group of symmetry to the dynamics of a constrained chain

Subject of this work are the applications of a field theoretical model, called here generalized nonlinear sigma model or simply GNLSM,to the dynamics of a chain subjected to constraints. Chains with similar properties and constraints have been discussed in a seminal paper of Edwards and Goodyear using an approach based on the Langevin equation. The GNLSM has been proposed in a previous publication in order to describe the dynamics of a two dimensional chain. In this paper the model is extended to d dimensions and a bending energy term is added to its action. As an application, two observables are computed in the case of a very stiff chain. The first observable is the dynamical form factor of a ring shaped chain. The second observable is a straightforward generalization to dynamics of the static form factor. This observable is relevant in order to estimate the average distance between two arbitrary points of the chain. Finally, a variant of the GNLNM is presented, in which the topological conditions which constrain the motion of two linked chains are imposed with the help of the Gauss linking invariant.

cond-mat.soft↗

arXiv2008

Dynamics of a stretched nonlinear polymer chain

We study the relaxation dynamics of a coarse-grained polymer chain at different degrees of stretching by both analytical means and numerical simulations. The macromolecule is modelled as a string of beads, connected by anharmonic springs, subject to a tensile force applied at the end monomer of the chain while the other end is fixed at the origin of coordinates. The impact of bond non-linearity on the relaxation dynamics of the polymer at different degrees of stretching is treated analytically within the Gaussian self-consistent approach (GSC) and then compared to simulation results derived from two different methods: Monte-Carlo (MC) and Molecular Dynamics (MD). At low and medium degrees of chain elongation we find good agreement between GSC predictions and the Monte-Carlo simulations. However, for strongly stretched chains the MD method, which takes into account inertial effects, reveals two important aspects of the nonlinear interaction between monomers: (i) a coupling and energy transfer between the damped, oscillatory normal modes of the chain, and (ii) the appearance of non-vanishing contributions of a continuum of frequencies around the characteristic modes in the power spectrum of the normal mode correlation functions.

cond-mat.soft↗

arXiv2008

Adsorption Kinetics of a Single Polymer on a Solid Plane

We study analytically and by means of an off-lattice bead-spring dynamic Monte Carlo simulation model the adsorption kinetics of a single macromolecule on a structureless flat substrate in the regime of strong physisorption. The underlying notion of a ``stem-flower'' polymer conformation, and the related mechanism of ``zipping'' during the adsorption process are shown to lead to a Fokker-Planck equation with reflecting boundary conditions for the time-dependent probability distribution function (PDF) of the number of adsorbed monomers. The theoretical treatment predicts that the mean fraction of adsorbed segments grows with time as a power law with a power of $(1+ν)^{-1}$ where $ν\approx 3/5$ is the Flory exponent. The instantaneous distribution of train lengths is predicted to follow an exponential relationship. The corresponding PDFs for loops and tails are also derived. The complete solution for the time-dependent PDF of the number of adsorbed monomers is obtained numerically from the set of discrete coupled differential equations and shown to be in perfect agreement with the Monte Carlo simulation results. In addition to homopolymer adsorption, we study also regular multiblock copolymers and random copolymers, and demonstrate that their adsorption kinetics may be considered within the same theoretical model.

cond-mat.soft↗

arXiv2007

Polymer translocation through a nanopore - a showcase of anomalous diffusion

The translocation dynamics of a polymer chain through a nanopore in the absence of an external driving force is analyzed by means of scaling arguments, fractional calculus, and computer simulations. The problem at hand is mapped on a one dimensional {\em anomalous} diffusion process in terms of reaction coordinate $s$ (i.e. the translocated number of segments at time $t$) and shown to be governed by an universal exponent $α= 2/(2ν+2-γ_1)$ whose value is nearly the same in two- and three-dimensions. The process is described by a {\em fractional} diffusion equation which is solved exactly in the interval $0 $, and $ - < s(t)>^2$ which provide full description of the diffusion process. The comparison of the analytic results with data derived from extensive Monte Carlo (MC) simulations reveals very good agreement and proves that the diffusion dynamics of unbiased translocation through a nanopore is anomalous in its nature.

cond-mat.soft↗

arXiv2007

Driven polymer translocation through a nanopore: a manifestation of anomalous diffusion

We study the translocation dynamics of a polymer chain threaded through a nanopore by an external force. By means of diverse methods (scaling arguments, fractional calculus and Monte Carlo simulation) we show that the relevant dynamic variable, the translocated number of segments $s(t)$, displays an {\em anomalous} diffusive behavior even in the {\em presence} of an external force. The anomalous dynamics of the translocation process is governed by the same universal exponent $α= 2/(2ν+2 - γ_1)$, where $ν$ is the Flory exponent and $γ_1$ - the surface exponent, which was established recently for the case of non-driven polymer chain threading through a nanopore. A closed analytic expression for the probability distribution function $W(s, t)$, which follows from the relevant {\em fractional} Fokker - Planck equation, is derived in terms of the polymer chain length $N$ and the applied drag force $f$. It is found that the average translocation time scales as $τ\propto f^{-1}N^{\frac{2}α -1}$. Also the corresponding time dependent statistical moments, $< s(t) > \propto t^α$ and $< s(t)^2 > \propto t^{2α}$ reveal unambiguously the anomalous nature of the translocation dynamics and permit direct measurement of $α$ in experiments. These findings are tested and found to be in perfect agreement with extensive Monte Carlo (MC) simulations.

cond-mat.stat-mech↗

arXiv2006

Field - Driven Translocation of Regular Block Copolymers through a Selective Liquid - Liquid Interface

We propose a simple scaling theory describing the variation of the mean first passage time (MFPT) $τ(N,M)$ of a regular block copolymer of chain length $N$ and block size $M$ which is dragged through a selective liquid-liquid interface by an external field $B$. The theory predicts a non-Arrhenian $τ$ vs. $B$ relationship which depends strongly on the size of the blocks, $M$, and rather weakly on the total polymer length, $N$. The overall behavior is strongly influenced by the degree of selectivity between the two solvents $χ$. The variation of $τ(N,M)$ with $N$ and $M$ in the regimes of weak and strong selectivity of the interface is also studied by means of computer simulations using a dynamic Monte Carlo coarse-grained model. Good qualitative agreement with theoretical predictions is found. The MFPT distribution is found to be well described by a $Γ$ - distribution. Transition dynamics of ring- and telechelic polymers is also examined and compared to that of the linear chains. The strong sensitivity of the ``capture'' time $τ(N,M)$ with respect to block length $M$ suggests a possible application as a new type of chromatography designed to separate and purify complex mixtures with different block sizes of the individual macromolecules.

cond-mat.soft↗

arXiv2006

Kinetics of copolymer localization at a selective liquid-liquid interface

The localization kinetics of a regular block-copolymer of total length $N$ and block size $M$ at a selective liquid-liquid interface is studied in the limit of strong segregation between hydrophobic and polar segments in the chain. We propose a simple analytic theory based on scaling arguments which describes the relaxation of the initial coil into a flat-shaped layer for the cases of both Rouse and Zimm dynamics. For Rouse dynamics the characteristic times for attaining equilibrium values of the gyration radius components perpendicular and parallel to the interface are predicted to scale with block length $M$ and chain length $N$ as $τ_{\perp} \propto M^{1+2ν}$ (here $ν\approx 0.6$ is the Flory exponent) and as $τ_{\parallel} \propto N^2$, although initially the characteristic coil flattening time is predicted to scale with block size as $\propto M$. Since typically $N\gg M$ for multiblock copolymers, our results suggest that the flattening dynamics proceeds faster perpendicular rather than parallel to the interface, in contrast to the case of Zimm dynamics where the two components relax with comparable rate, and proceed considerably slower than in the Rouse case. We also demonstrate that, in the case of Rouse dynamics, these scaling predictions agree well with the results of Monte Carlo simulations of the localization dynamics. A comparison to the localization dynamics of {\em random} copolymers is also carried out.

cond-mat.soft↗

arXiv2006

Aggregates of rod-coil diblock copolymers adsorbed at a surface

The behaviour of rod-coil diblock copolymers close to a surface is discussed by using extended scaling methods. The copolymers are immersed in selective solvent such that the rods are likely to aggregate to gain energy. The rods are assumed to align only parallel to each other, such that they gain a maximum energy by forming liquid crystalline structures. If an aggregate of these copolymers adsorbs with the rods parallel to the surface the rods shift with respect to each other to allow for the chains to gain entropy. It is shown that this shift decays with increasing distance from the surface. The profile of this decay away from the surface is calculated by minimisation of the total free energy of the system. The stability of such an adsorbed aggregate and other possible configurations are discussed as well.

cond-mat.soft↗

arXiv2003

Dynamics of a polymer in a quenched random medium: A Monte Carlo investigation

We use an off - lattice bead - spring model of a self - avoiding polymer chain immersed in a 3-dimensional quenched random medium to study chain dynamics by means of a Monte - Carlo (MC) simulation. The chain center of mass mean-squared displacement as a function of time reveals two crossovers which depend both on chain length $N$ and on the degree of Gaussian disorder $Δ$. The first one from normal to anomalous diffusion regime is found at short time $τ_1$ and observed to vanish rapidly as $τ_1 \propto Δ^{- 11}$ with growing disorder. The second crossover back to normal diffusion, $τ_2$, scales as $τ_2 \propto N^{2ν+ 1} f(N^{2-3ν}Δ)$ with $f$ being some scaling function. The diffusion coefficient $D_N$ depends strongly on disorder and drops dramatically at a {\em critical dispersion} $Δ_{c} \propto N^{-2 + 3ν}$ of the disorder potential so that for $Δ> Δ_c$ the chain center of mass is practically frozen.The time-dependent Rouse modes correlation function $C_{p}(t)$ reveals a characteristic plateau at $Δ> Δ_c$ which is the hallmark of a non - ergodic regime. These findings agree well with our recent theoretical predictions.

cond-mat.soft↗

arXiv2002

Collapse or Swelling Dynamics of Homopolymer Rings: Self-consistent Hartree approach

We investigate by the use of the Martin - Siggia - Rose generating functional technique and the self - consistent Hartree approximation, the dynamics of the ring homopolymer collapse (swelling) following an instantaneous change into a poor (good) solvent conditions.The equation of motion for the time dependent monomer - to - monomer correlation function is systematically derived. It is argued that for describing of the coarse - graining process (which neglects the capillary instability and the coalescence of ``pearls'') the Rouse mode representation is very helpful, so that the resulting equations of motion can be simply solved numerically. In the case of the collapse this solution is analyzed in the framework of the hierarchically crumpled fractal picture, with crumples of successively growing scale along the chain. The presented numerical results are in line with the corresponding simple scaling argumentation which in particular shows that the characteristic collapse time of a segment of length $g$ scales as $t^* \sim ζ_0 g/τ$ (where $ζ_0$ is a bare friction coefficient and $τ$ is a depth of quench). In contrast to the collapse the globule swelling can be seen (in the case that topological effects are neglected) as a homogeneous expansion of the globule interior. The swelling of each Rouse mode as well as gyration radius $R_g$ is discussed.

cond-mat.soft↗

arXiv2001

Self- generated disorder and structural glass formation in homopolymer globules

We have investigated the interrelation between the spin glasses and the structural glasses. Spin glasses in this case are random magnets without reflection symmetry (e.g. $p$ - spin interaction spin glasses and Potts glasses) which contain quenched disorder, whereas the structural glasses are here exemplified by the homopolymeric globule, which can be viewed as a liquid of connected molecules on nano scales. It is argued that the homopolymeric globule problem can be mapped onto a disorder field theoretical model whose effective Hamiltonian resembles the corresponding one for the spin glass model. In this sense the disorder in the globule is self - generated (in contrast to spin glasses) and can be related with competitive interactions (virial coefficients of different signs) and the chain connectivity. The work is aimed at giving a quantitative description of this analogy. We have investigated the phase diagram of the homopolymeric globule where the transition line from the liquid to glassy globule is treated in terms of the replica symmetry breaking paradigm. The configurational entropy temperature dependence is also discussed.

cond-mat.stat-mech↗

arXiv2001

Weak violation of universality for Polyelectrolyte Chains: Variational Theory and Simulations

A variational approach is considered to calculate the free energy and the conformational properties of a polyelectrolyte chain in $d$ dimensions. We consider in detail the case of pure Coulombic interactions between the monomers, when screening is not present, in order to compute the end-to-end distance and the asymptotic properties of the chain as a function of the polymer chain length $N$. We find $R \simeq N^ν(\log N)^γ$ where $ν= \frac{3}{λ+2}$ and $λ$ is the exponent which characterize the long-range interaction $U \propto 1/r^λ$. The exponent $γ$ is shown to be non-universal, depending on the strength of the Coulomb interaction. We check our findings, by a direct numerical minimization of the variational energy for chains of increasing size $2^4<N<2^{15}$. The electrostatic blob picture, expected for small enough values of the interaction strength, is quantitatively described by the variational approach. We perform a Monte Carlo simulation for chains of length $2^4<N<2^{10}$. The non universal behavior of the exponent $ γ$ previously derived within the variational method, is also confirmed by the simulation results. Non-universal behavior is found for a polyelectrolyte chain in $d=3$ dimension. Particular attention is devoted to the homopolymer chain problem, when short range contact interactions are present.

cond-mat.soft↗

arXiv2000

Slow plasmon modes in polymeric salt solutions

The dynamics of polymeric salt solutions are presented. The salt consists of chains $\rm A$ and $\rm B$, which are chemically different and interact with a Flory-interaction parameter $χ$, the $\rm A$ chain ends carry a positive charge whereas the $\rm B$ chain ends are modified by negative charges. The static structure factor shows a peak corresponding to a micro phase separation. At low momentum transfer, the interdiffusion mode is driven by electrostatics and is of the plasmon-type, but with an unusually low frequency, easily accessible by experiments. This is due to the polymer connectivity that introduces high friction and amplifies the charge scattering thus allowing for low charge densities. The interdiffusion mode shows a minimum (critical slowing down) at finite $k$ when the interaction parameter increases we find then a low $k$ frequency quasi-plateau.

cond-mat.soft↗

arXiv2000

Polyelectrolyte gels in poor solvent: Equilibrium and non equilibrium elasticity

We study theoretically using scaling arguments the behavior of polyelectrolyte gels in poor solvents. Following the classical picture of Katchalsky, our approach is based on single chain elasticity but it accounts for the recently proposed pearl-necklace structure of polyelectrolytes in poor solvents. The elasticity both of gels at swelling equilibrium and of partially swollen, non equilibrium, gels is studied when parameters such as the ionic strength or the fraction of charged monomers are varied. Our theory could be useful to interpret recent experiments performed in Strasbourg that show that if identical gel samples are swollen to the same extent at different pH the sample with the highest charge has the lowest shear modulus.

cond-mat.soft↗

arXiv2000

Dynamics of structural models with a long-range interaction: glassy versus non-glassy behavior

By making use of the Langevin dynamics and its generating functional (GF) formulation the influence of the long-range nature of the interaction on the tendency of the glass formation is systematically investigated. In doing so two types of models is considered: (i) the non-disordered model with a pure repulsive type of interaction and (ii) the model with a randomly distributed strength of interaction (a quenched disordered model). The long-ranged potential of interaction is scaled with a number of particles $N$ in such a way as to enable for GF the saddle-point treatment as well as the systematic 1/N - expansion around it. We show that the non-disordered model has no glass transition which is in line with the mean-field limit of the mode - coupling theory (MCT) predictions. On the other hand the model with a long-range interaction which above that has a quenched disorder leads to MC - equations which are generic for the $p$ - spin glass model and polymeric manifold in a random media.

cond-mat.stat-mech↗

arXiv2000

Stretching necklaces

Polyelectrolytes in poor solvents show a necklace structure where collapsed polymer pearls are linked to stretched strings. In the present paper the elasticity of such chains is studied in detail. Different deformation regimes are addressed. The first is the continuous regime, where many pearls are present. A continuous force extension relation ship is calculated. The main contribution comes from the tension balance and the electrostatic repulsion of consecutive pearls. The main correction term stems from the finite size of the pearls, which monitors their surface energy. For a finite amount of pearls discontinuous stretching is predicted. Finally counterion effects are discussed qualitatively.

cond-mat.soft↗

arXiv1999

How to break the replica symmetry in structural glasses

The variational principle (VP) has been used to capture the metastable states of a glass-forming molecular system without quenched disorder. It has been shown that VP naturally leads to a self-consistent random field Ginzburg-Landau model (RFGLM). In the framework of one-step replica symmetry breaking (1-RSB) the general solution of RFGLM is discussed in the vicinity of the spinodal temperature T_{A} in terms of ``hidden'' formfactors $\tilde g(k)$, g_{0}(k) and $Δ(k)$. The self-generated disorder spontaneously arises. It is argued that at T < T_{A} the activated dynamics is dominant.

cond-mat.dis-nn↗

arXiv1999

Mean-Field-Theory for Polymers in Mixed Solvents Thermodynamic and Structural Properties

Theoretical aspects of polymers in mixed solvents are considered using the Edwards Hamiltonian formalism. Thermodynamic and structural properties are investigated and some predictions are made when the mixed solvent approaches criticality. Both the single and the many chain problems are examined. When the pure mixed solvent is near criticality, addition of a small amount of polymers shifts the criticality towards either enhanced compatibility or induced phase separation depending upon the value of the parameter describing the interaction asymmetry of the solvents with respect to the polymer. The polymer-solvent effective interaction parameter increases strongly when the solvent mixture approaches criticality. Accordingly, the apparent excluded volume parameter decreases and may vanish or even become negative. Consequently, the polymer undergoes a phase transition from a swollen state to an unperturbed state or even take a collapsed configuration. The effective potential acting on a test chain in strong solutions is calculated and the concept of Edwards screening discussed. Structural properties of ternary mixtures of polymers in mixed solvents are investigated within the Edwards Hamiltonian model. It is shown that the effective potential on a test chain in strong solutions could be written as an infinite series expansion of terms describing interactions via one chain, two chains etc. This summation can be performed following a similar scheme as in the Ornstein-Zernike series expansion.

cond-mat.soft↗