arXiv subjects

Kurt Binder

Publications and source records attributed to Kurt Binder.

At least 37 records · Page 2Linked to original sources

arXiv2014

Logarithmic Finite-Size Effects on Interfacial Free Energies: Phenomenological Theory and Monte Carlo Studies

The computation of interfacial free energies between coexisting phases (e.g.~saturated vapor and liquid) by computer simulation methods is still a challenging problem due to the difficulty of an atomistic identification of an interface, and due to interfacial fluctuations on all length scales. The approach to estimate the interfacial tension from the free energy excess of a system with interfaces relative to corresponding single-phase systems does not suffer from the first problem but still suffers from the latter. Considering $d$-dimensional systems with interfacial area $L^{d-1}$ and linear dimension $L_z$ in the direction perpendicular to the interface, it is argued that the interfacial fluctuations cause logarithmic finite-size effects of order $\ln (L) / L^{d-1}$ and order $\ln (L_z)/L ^{d-1}$, in addition to regular corrections (with leading order $\text{const}/L^{d-1}$). A phenomenological theory predicts that the prefactors of the logarithmic terms are universal (but depend on the applied boundary conditions and the considered statistical ensemble). The physical origin of these corrections are the translational entropy of the interface as a whole, "domain breathing" (coupling of interfacial fluctuations to the bulk order parameter fluctuations of the coexisting domains), and capillary waves. Using a new variant of the ensemble switch method, interfacial tensions are found from Monte Carlo simulations of $d=2$ and $d=3$ Ising models and a Lennard Jones fluid. The simulation results are fully consistent with the theoretical predictions.

cond-mat.stat-mech↗

arXiv2014

Determination of the origin and magnitude of logarithmic finite-size effects on interfacial tension: Role of interfacial fluctuations and domain breathing

The ensemble-switch method for computing wall excess free energies of condensed matter is extended to estimate the interface free energies between coexisting phases very accurately. By this method, system geometries with linear dimensions $L$ parallel and $L_z$ perpendicular to the interface with various boundary conditions in the canonical or grandcanonical ensemble can be studied. Using two- and three-dimensional Ising models, the nature of the occurring logarithmic finite size corrections is studied. It is found crucial to include interfacial fluctuations due to "domain breathing".

cond-mat.stat-mech↗

arXiv2014

Conformations, Transverse Fluctuations and Crossover Dynamics of a Semi-Flexible Chain in Two Dimensions

We present a unified scaling description for the dynamics of monomers of a semiflexible chain under good solvent condition in the free draining limit. We consider both the cases where the contour length $L$ is comparable to the persistence length $\ell_p$ and the case $L\gg \ell_p$. Our theory captures the early time monomer dynamics of a stiff chain characterized by $t^{3/4}$ dependence for the mean square displacement(MSD) of the monomers, but predicts a first crossover to the Rouse regime of $t^{2ν/{1+2ν}}$ for $τ_1 \sim \ell_p^3$, and a second crossover to the purely diffusive dynamics for the entire chain at $τ_2 \sim L^{5/2}$. We confirm the predictions of this scaling description by studying monomer dynamics of dilute solution of semi-flexible chains under good solvent conditions obtained from our Brownian dynamics (BD) simulation studies for a large choice of chain lengths with number of monomers per chain N = 16 - 2048 and persistence length $\ell_p = 1 - 500$ Lennard-Jones (LJ) units. These BD simulation results further confirm the absence of Gaussian regime for a 2d swollen chain from the slope of the plot of $\langle R_N^2 \rangle/2L \ell_p \sim L/\ell_p$ which around $L/\ell_p \sim 1$ changes suddenly from $\left(L/\ell_p \right) \rightarrow \left(L/\ell_p \right)^{0.5} $, also manifested in the power law decay for the bond autocorrelation function disproving the validity of the WLC in 2d. We further observe that the normalized transverse fluctuations of the semiflexible chains for different stiffness $\sqrt{\langle l_{\bot}^2\rangle}/L$ as a function of renormalized contour length $L/\ell_p$ collapse on the same master plot and exhibits power law scaling $\sqrt{\langle l_{\bot}^2\rangle}/L \sim (L/\ell_p)^η$ at extreme limits, where $η= 0.5$ for extremely stiff chains ($L/\ell_p \gg 1$), and $η= -0.25$ for fully flexible chains.

physics.bio-ph↗

arXiv2014

Phase Behavior of Active Swimmers in Depletants: Molecular Dynamics and Integral Equation Theory

We study the structure and phase behavior of a binary mixture where one of the components is self-propelling in nature. The inter-particle interactions in the system were taken from the Asakura-Oosawa model, for colloid-polymer mixtures, for which the phase diagram is known. In the current model version the colloid particles were made active using the Vicsek model for self-propelling particles. The resultant active system was studied by molecular dynamics methods and integral equation theory. Both methods produce results consistent with each other and demonstrate that the Vicsek model based activity facilitates phase separation, thus broadening the coexistence region.

cond-mat.stat-mech↗

arXiv2014

Unconventional ordering behavior of semi-flexible polymers in dense brushes under compression

Using a coarse-grained bead-spring model for semi-flexible macromolecules forming a polymer brush, structure and dynamics of the polymers is investigated, varying chain stiffness and grafting density. The anchoring condition for the grafted chains is chosen such that their first bonds are oriented along the normal to the substrate plane. Compression of such a semi-flexible brush by a planar piston is observed to be a two-stage process: for small compressions the chains contract by "buckling" deformation whereas for larger compression the chains exhibit a collective (almost uniform) bending deformation. Thus, the stiff polymer brush undergoes a 2-nd order phase transition of collective bond reorientation. The pressure, required to keep the stiff brush at a given degree of compression, is thereby significantly smaller than for an otherwise identical brush made of entirely flexible polymer chains! While both the brush height and the chain linear dimension in the z-direction perpendicular to the substrate increase monotonically with increasing chain stiffness, lateral (xy) chain linear dimensions exhibit a maximum at intermediate chain stiffness. Increasing the grafting density leads to a strong decrease of these lateral dimensions, compatible with an exponential decay. Also the recovery kinetics after removal of the compressing piston is studied, and found to follow a power-law / exponential decay with time. A simple mean-field theoretical consideration, accounting for the buckling/bending behavior of semi-flexible polymer brushes under compression, is suggested.

cond-mat.soft↗

arXiv2013

Non mean-field behaviour of critical wetting transition for short-range forces

Critical wetting transition for short-range forces in three dimensions ($d=3$) is reinvestigated by means of Monte Carlo simulation. Using anisotropic finite size scaling approach, as well as approaches that do not rely on finite size scaling, we show that the critical wetting transition shows clear deviation from mean-field behaviour. We estimate that the effective critical exponent $ν_{\|}^{\textrm{eff}}=1.76\pm 0.08$ for $J/kT=0.35$ and $ν_{\|}^{\textrm{eff}}=1.85\pm 0.07$ for $J/kT=0.25$. These values are in accord with predictions of Parry {\it et al.} [Phys. Rev. Lett. {\bf 100}, 136105 (2008)]. We also point out that the anisotropic finite size scaling approach in $d=3$ requires additional modification in order to reach full consistency of simulational results.

cond-mat.stat-mech↗

arXiv2013

Universal monomer dynamics of a two dimensional semi-flexible chain

We present a unified scaling theory for the dynamics of monomers for dilute solutions of semiflexible polymers under good solvent conditions in the free draining limit. Our theory encompasses the well-known regimes of mean square displacements (MSDs) of stiff chains growing like t^{3/4} with time due to bending motions, and the Rouse-like regime t^{2 ν/ (1+ 2ν)} where νis the Flory exponent describing the radius R of a swollen flexible coil. We identify how the prefactors of these laws scale with the persistence length l_p, and show that a crossover from stiff to flexible behavior occurs at a MSD of order l^2_p (at a time proportional to l^3_p). A second crossover (to diffusive motion) occurs when the MSD is of order R^2. Large scale Molecular Dynamics simulations of a bead-spring model with a bond bending potential (allowing to vary l_p from 1 to 200 Lennard-Jones units) provide compelling evidence for the theory, in D=2 dimensions where ν=3/4. Our results should be valuable for understanding the dynamics of DNA (and other semiflexible biopolymers) adsorbed on substrates.

cond-mat.soft↗

arXiv2013

Monte Carlo Tests of Nucleation Concepts in the Lattice Gas Model

The conventional theory of homogeneous and heterogeneous nucleation in a supersaturated vapor is tested by Monte Carlo simulations of the lattice gas (Ising) model with nearest-neighbor attractive interactions on the simple cubic lattice. The theory considers the nucleation process as a slow (quasi-static) cluster (droplet) growth over a free energy barrier $ΔF^*$, constructed in terms of a balance of surface and bulk term of a "critical droplet" of radius $R^*$, implying that the rates of droplet growth and shrinking essentially balance each other for droplet radius $R=R^*$. For heterogeneous nucleation at surfaces, the barrier is reduced by a factor depending on the contact angle. Using the definition of "physical" clusters based on the Fortuin-Kasteleyn mapping, the time-dependence of the cluster size distribution is studied for "quenching experiments" in the kinetic Ising model, and the cluster size $\ell ^*$ where the cluster growth rate changes sign is estimated. These studies of nucleation kinetics are compared to studies where the relation between cluster size and supersaturation is estimated from equilibrium simulations of phase coexistence between droplet and vapor in the canonical ensemble. The chemical potential is estimated from a lattice version of the Widom particle insertion method. For large droplets it is shown that the "physical clusters" have a volume consistent with the estimates from the lever rule. "Geometrical clusters" (defined such that each site belonging to the cluster is occupied and has at least one occupied neighbor site) yield valid results only for temperatures less than 60% of the critical temperature, where the cluster shape is non-spherical. We show how the chemical potential can be used to numerically estimate $ΔF^*$ also for non-spherical cluster shapes.

cond-mat.soft↗

arXiv2013

Estimation of Persistence Lengths of Semiflexible Polymers: Insight from Simulations

The persistence length of macromolecules is one of their basic characteristics, describing their intrinsic local stiffness. However, it is difficult to extract this length from physical properties of the polymers, different recipes may give answers that disagree with each other. Monte Carlo simulations are used to elucidate this problem, giving a comparative discussion of two lattice models, the self-avoiding walk model extended by a bond bending energy, and bottle-brush polymers described by the bond fluctuation model. The conditions are discussed under which a description of such macromolecules by Kratky-Porod worm-like chains holds, and the question to what extent the persistence length depends on external conditions (such as solvent quality) is considered. The scattering function of semiflexible polymers is discussed in detail, a comparison to various analytic treatments is given, and an outlook to experimental work is presented.

cond-mat.soft↗

arXiv2012

Scattering function of semiflexible polymer chains under good solvent conditions

Using the pruned-enriched Rosenbluth Monte Carlo algorithm, the scattering functions of semiflexible macromolecules in dilute solution under good solvent conditions are estimated both in $d=2$ and $d=3$ dimensions, considering also the effect of stretching forces. Using self-avoiding walks of up to $N = 25600$ steps on the square and simple cubic lattices, variable chain stiffness is modeled by introducing an energy penalty $ε_b$ for chain bending; varying $q_b=\exp (- ε_b/k_BT)$ from $q_b=1$ (completely flexible chains) to $q_b = 0.005$, the persistence length can be varied over two orders of magnitude. For unstretched semiflexible chains we test the applicability of the Kratky-Porod worm-like chain model to describe the scattering function, and discuss methods for extracting persistence length estimates from scattering. While in $d=2$ the direct crossover from rod-like chains to self-avoiding walks invalidates the Kratky-Porod description, it holds in $d=3$ for stiff chains if the number of Kuhn segments $n_K$ does not exceed a limiting value $n^*_K$ (which depends on the persistence length). For stretched chains, the Pincus blob size enters as a further characteristic length scale. The anisotropy of the scattering is well described by the modified Debye function, if the actual observed chain extension $ $ (end-to-end distance in the direction of the force) as well as the corresponding longitudinal and transverse linear dimensions $ - ^2$, $ $ are used.

cond-mat.soft↗

arXiv2012

Wetting Transition in the Two-Dimensional Blume-Capel Model: A Monte Carlo study

The wetting transition of the Blume-Capel model is studied by a finite-size scaling analysis of $L \times M$ lattices where competing boundary fields $\pm H_1$ act on the first row or last row of the $L$ rows in the strip, respectively. We show that using the appropriate anisotropic version of finite size scaling, critical wetting in $d=2$ is equivalent to a "bulk" critical phenomenon with exponents $α=-1$, $β=0$, and $γ=3$. These concepts are also verified for the Ising model. For the Blume-Capel model it is found that the field strength $H_{1c} (T)$ where critical wetting occurs goes to zero when the bulk second-order transition is approached, while $H_{1c}(T)$ stays nonzero in the region where in the bulk a first-order transition from the ordered phase, with nonzero spontaneous magnetization, to the disordered phase occurs. Interfaces between coexisting phases then show interfacial enrichment of a layer of the disordered phase which exhibits in the second order case a finite thickness only. A tentative discussion of the scaling behavior of the wetting phase diagram near the tricritical point also is given.

cond-mat.stat-mech↗

arXiv2012

Simulation of fluid-solid coexistence in finite volumes: A method to study the properties of wall-attached crystalline nuclei

The Asakura-Oosawa model for colloid-polymer mixtures is studied by Monte Carlo simulations at densities inside the two-phase coexistence region of fluid and solid. Choosing a geometry where the system is confined between two flat walls, and a wall-colloid potential that leads to incomplete wetting of the crystal at the wall, conditions can be created where a single nanoscopic wall-attached crystalline cluster coexists with fluid in the remainder of the simulation box. Following related ideas that have been useful to study heterogeneous nucleation of liquid droplets at the vapor-liquid coexistence, we estimate the contact angles from observations of the crystalline clusters in thermal equilibrium. We find fair agreement with a prediction based on Young's equation, using estimates of interface and wall tension from the study of flat surfaces. It is shown that the pressure versus density curve of the finite system exhibits a loop, but the pressure maximum signifies the "droplet evaporation-condensation" transition and thus has nothing in common with a van der Waals-like loop. Preparing systems where the packing fraction is deep inside the two-phase coexistence region, the system spontaneously forms a "slab state", with two wall-attached crystalline domains separated by (flat) interfaces from liquid in full equilibrium with the crystal in between; analysis of such states allows a precise estimation of the bulk equilibrium properties at phase coexistence.

cond-mat.soft↗

arXiv2012

Transitions between imperfectly ordered crystalline structures: A phase switch Monte Carlo study

A model for two-dimensional colloids confined laterally by "structured boundaries" (i.e., ones that impose a periodicity along the slit) is studied by Monte Carlo simulations. When the distance D between the confining walls is reduced at constant particle number from an initial value D_0, for which a crystalline structure commensurate with the imposed periodicity fits, to smaller values, a succession of phase transitions to imperfectly ordered structures occur. These structures have a reduced number of rows parallel to the boundaries (from n to n-1 to n-2 etc.) and are accompanied by an almost periodic strain pattern, due to "soliton staircases" along the boundaries. Since standard simulation studies of such transitions are hampered by huge hysteresis effects, we apply the phase switch Monte Carlo method to estimate the free energy difference between the structures as a function of the misfit between D and D_0, thereby locating where the transitions occurs in equilibrium. For comparison, we also obtain this free energy difference from a thermodynamic integration method: the results agree, but the effort required to obtain the same accuracy as provided by phase switch Monte Carlo would be at least three orders of magnitude larger. We also show for a situation where several "candidate structures" exist for a phase, that phase switch Monte Carlo can clearly distinguish the metastable structures from the stable one. Finally, applying the method in the conjugate statistical ensemble (where the normal pressure conjugate to D is taken as an independent control variable) we show that the standard equivalence between the conjugate ensembles of statistical mechanics is violated.

cond-mat.stat-mech↗

arXiv2011

Stretching Semiflexible Polymer Chains: Evidence for the Importance of Excluded Volume Effects from Monte Carlo Simulation

Semiflexible macromolecules in dilute solution under very good solvent conditions are modeled by self-avoiding walks on the simple cubic lattice ($d=3$ dimensions) and square lattice ($d=2$ dimensions), varying chain stiffness by an energy penalty $ε_b$ for chain bending. In the absence of excluded volume interactions, the persistence length $\ell_p$ of the polymers would then simply be $\ell_p=\ell_b(2d-2)^{-1}q_b^{-1}$ with $q_b= \exp(-ε_b/k_BT)$, the bond length $\ell_b$ being the lattice spacing, and $k_BT$ is the thermal energy. Using Monte Carlo simulations applying the pruned-enriched Rosenbluth method (PERM), both $q_b$ and the chain length $N$ are varied over a wide range $(0.005 \leq q_b \leq 1, \; N \leq 50000$), and also a stretching force $f$ is applied to one chain end (fixing the other end at the origin). In the absence of this force, in $d=2$ a single crossover from rod-like behavior (for contour lengths less than $\ell_p$) to swollen coils occurs, invalidating the Kratky-Porod model, while in $d=3$ a double crossover occurs, from rods to Gaussian coils (as implied by the Kratky-Porod model) and then to coils that are swollen due to the excluded volume interaction. If the stretching force is applied, excluded volume interactions matter for the force versus extension relation irrespective of chain stiffness in $d=2$, while theories based on the Kratky-Porod model are found to work in $d=3$ for stiff chains in an intermediate regime of chain extensions. While for $q_b \ll 1$ in this model a persistence length can be estimated from the initial decay of bond-orientational correlations, it is argued that this is not possible for more complex wormlike chains (e.g. bottle-brush polymers). Consequences for the proper interpretation of experiments are briefly discussed.

cond-mat.soft↗

arXiv2011

Breakdown of the Kratky-Porod Wormlike Chain Model for Semiflexible Polymers in Two Dimensions

By large-scale Monte Carlo simulations of semiflexible polymers in $d=2$ dimensions the applicability of the Kratky-Porod model is tested. This model is widely used as "standard model" for describing conformations and force versus extension curves of stiff polymers. It is shown that semiflexible polymers in $d=2$ show a crossover from hard rods to self-avoiding walks, the intermediate Gaussian regime (implied by the Kratky-Porod model) is completely absent. Hence the latter can also describe force versus extension curves only if the contour length is only a few times larger than the persistence length. Consequences for experiments on biopolymers at interfaces are briefly discussed.

cond-mat.soft↗

arXiv2011

Computer simulation of bottle brush polymers with flexible backbone: Good solvent versus Theta solvent conditions

By Molecular Dynamics simulation of a coarse-grained bead-spring type model for a cylindrical molecular brush with a backbone chain of $N_b$ effective monomers to which with grafting density $σ$ side chains with $N$ effective monomers are tethered, several characteristic length scales are studied for variable solvent quality. Side chain lengths are in the range $5 \le N \le 40$, backbone chain lengths are in the range $50 \le N_b \le 200$, and we perform a comparison to results for the bond fluctuation model on the simple cubic lattice (for which much longer chains are accessible, $N_b \le 1027$, and which corresponds to an athermal, very good, solvent). We obtain linear dimensions of side chains and the backbone chain and discuss their $N$-dependence in terms of power laws and the associated effective exponents. We show that even at the Theta point the side chains are considerably stretched, their linear dimension depending on the solvent quality only weakly. Effective persistence lengths are extracted both from the orientational correlations and from the backbone end-to-end distance; it is shown that different measures of the persistence length (which would all agree for Gaussian chains) are not mutually consistent with each other, and depend distinctly both on $N_b$ and the solvent quality. A brief discussion of pertinent experiments is given.

cond-mat.soft↗

arXiv2011

Methods to Compute Pressure and Wall Tension in Fluids containing Hard Particles

Colloidal systems are often modelled as fluids of hard particles (possibly with an additional soft attraction, e.g. caused by polymers also contained in the suspension). in simulations of such systems, the virial theorem cannot be straightforwardly applied to obtain the components of the pressure tensor. In systems confined by walls, it is hence also not straightforward to extract the excess energy due to the wall (the "wall tension") from the pressure tensor anisotropy. A comparative evaluation of several methods to circumvent this problem is presented, using as examples fluids of hard spheres and the Asakura-Oosawa model of colloid-polymer mixtures with a size ratio $q=0.15$ (for which the effect of the polymers can be integrated out to yield an effective attractive potential between the colloids). Factors limiting the accuracy of the various methods are carefully discussed, and controlling these factors very good mutual agreement between the various methods is found.

cond-mat.soft↗

arXiv2011

Mesophase formation in two-component cylindrical bottle-brush polymers

When two types of side chains (A,B) are densely grafted to a (stiff) backbone and the resulting bottle-brush polymer is in a solution under poor solvent conditions, an incompatibility between A and B leads to microphase separation in the resulting cylindrical brush. The possible types of ordering are reminiscent of the ordering of block copolymers in cylindrical confinement. Starting from this analogy, Leibler's theory of microphase separation in block copolymer melts is generalized to derive a description of the system in the weak segregation limit. Also molecular dynamics simulation results of a corresponding coarse-grained bead-spring model are presented. Using side chain lengths up to N = 50 effective monomers, the ratio of the Lennard-Jones energy parameter between unlike monomers $(ε_{AB})$ and monomers of the same kind $(ε_{AA} = ε_{BB})$ is varied. Various correlation functions are analyzed to study the conditions when (local) Janus cylinder-type ordering and when (local) microphase separation in the direction along the cylinder axis occurs. Both the analytical theory and the simulations give evidence for short range order due to a tendency towards microphase separation in the axial direction, with a wavelength proportional to the side chain gyration radius, irrespective of temperature and grafting density, for a wide range of these parameters.

cond-mat.soft↗