We report a numerical study of the diffusiophoresis of short polymers using non-equilibrium molecular dynamics simulations. More precisely, we consider polymer chains in a fluid containing a solute which has a concentration gradient, and examine the variation of the induced diffusiophoretic velocity of the polymer chains as the interaction between the monomer and the solute is varied. We find that there is a non-monotonic relation between the diffusiophoretic mobility and the strength of the monomer-solute interaction. In addition we find a weak dependence of the mobility on the length of the polymer chain, which shows clear difference from the diffusiophoresis of a solid particle. Interestingly, the hydrodynamic flow through the polymer is much less screened than for pressure driven flows.
A colloidal particle placed in an inhomogeneous solution of smaller non-adsorbing polymers will move towards regions of lower polymer concentration, in order to reduce the free energy of the interface between the surface of the particle and the solution. This phenomenon is known as diffusiophoresis. Treating the polymer as penetrable hard spheres, as in the Asakura-Oosawa model, a simple analytic expression for the diffusiophoretic drift velocity can be obtained. In the context of drying films we show that diffusiophoresis by this mechanism can lead to stratification under easily accessible ex…
Nonequilibrium molecular dynamics simulations are used to investigate the influence of hydrodynamic interactions on vertical segregation (stratification) in drying mixtures of long and short polymer chains. In agreement with previous computer simulations and theoretical modeling, the short polymers stratify on top of the long polymers at the top of the drying film when hydrodynamic interactions between polymers are neglected. However, no stratification occurs at the same drying conditions when hydrodynamic interactions are incorporated through an explicit solvent model. Our analysis demonstrat…
Due to the complex characteristics of bottle-brush polymers, it became a challenge to develop an efficient algorithm for studying such macromolecules under various solvent conditions or some constraints in the space by using computer simulations. In the limit of a bottle-brush polymer with a rather stiff backbone (straight rigid backbone), we generalize the variant of the biased chain growth algorithm, the pruned-enriched Rosenbluth method, for simulating polymers with complex architecture, from star polymers to bottle-brush polymers, on the simple cubic lattice. With the high statistics of ou…
To study the cooling behavior and the glass transition of polymer melts in bulk and with free surfaces a coarse-grained weakly semi-flexible polymer model is developed. Based on a standard bead spring model with purely repulsive interactions an attractive potential between non-bonded monomers is added, such that the pressure of polymer melts is tuned to zero. Additionally, the commonly used bond bending potential [Everaers et al., Science 303, 823 (2004)] controlling the chain stiffness is replaced by a new bond bending potential. For this model, we show that the Kuhn length and the internal d…
Obtaining reliable estimates of the statistical properties of complex macromolecules by computer simulation is a task that requires high computational effort as well as the development of highly efficient simulation algorithms. We present here an algorithm combining local moves, the pivot algorithm, and an adjustable simulation lattice box for simulating dilute systems of bottle-brush polymers with a flexible backbone and flexible side chains under good solvent conditions. Applying this algorithm to the bond fluctuation model, very precise estimates of the mean square end-to-end distances and …
The advances in new technologies have prompted the need for functional systems smaller than the gyration radius of polymer chains. Thus, understanding how nanoconfinement affects polymer properties has been the focus of a lot of research for over a decade. Polystyrene in particular has been reported to be strongly affected when nanoconfined as a thin film and specifically its glass transition temperature (Tg) is reported to decrease with decreasing film thickness. Tremendous effort has been dedicated to developing methods for quantifying the large-scale dynamic of nanoconfined polymers: film d…
We study the effects of droplet finite size on the structure of nanogel particles synthesized by random crosslinking of molecular polymers diluted in nanoemulsions. For this, we use a bead-spring computer model of polymer-like structures that mimics the confined random crosslinking process corresponding to irradiation- or electrochemically-induced crosslinking methods. Our results indicate that random crosslinking under strong confinement can lead to unusual nanogel internal structures, with a central region less dense than the external one, whereas under moderate confinement the resulting str…
Capillary electrophoresis has long been been recognized as a powerful analytic tool. Here it is demonstrated that the same capillary electrophoretic experiments also reveal dynamic properties of the polymer solutions being used as the support medium. The dependence of the electrophoretic mobility on the size of the probe and the properties of the matrix polymers shows a unity of behavior between electrophoresis and other methods of studying polymer properties.
We use molecular dynamics simulations to investigate the microscopic and macroscopic response of model polymer networks to uniaxial elongations. By studying networks with strands lengths ranging from $N_s=20$ to 200 we cover the full crossover from cross-link to entanglement dominated behavior. Our results support a recent version of the tube model which accounts for the different strain dependence of chain localization due to chemical cross-links and entanglements.
Diffusion of long ring polymers in a melt is much slower than the reorganization of their internal structures. While direct evidences for entanglements have not been observed in the long ring polymers unlike linear polymer melts, threading between the rings is suspected to be the main reason for slowing down of ring polymer diffusion. It is, however, difficult to define the threading configuration between two rings because the rings have no chain end. In this work, evidences for threading dynamics of ring polymers are presented by using molecular dynamics simulation and applying a novel analys…
Compact polymers are self-avoiding random walks which visit every site on a lattice. This polymer model is used widely for studying statistical problems inspired by protein folding. One difficulty with using compact polymers to perform numerical calculations is generating a sufficiently large number of randomly sampled configurations. We present a Monte-Carlo algorithm which uniformly samples compact polymer configurations in an efficient manner allowing investigations of chains much longer than previously studied. Chain configurations generated by the algorithm are used to compute statistics …
Conventional molecular-dynamics (cMD) simulation has a well-known limitation in accessible time and length scales, and thus various enhanced sampling techniques have been proposed to alleviate the problem. In this paper we explore the utility of replica exchange with solute tempering (REST) (i.e., a variant of Hamiltonian replica exchange methods) to simulate the self-assembly of a supramolecular polymer in explicit solvent, and compare the performance with temperature-based replica exchange MD (T-REMD) as well as cMD. As a test system, we consider a relatively simple all-atom model of supramo…
The interplay between inter- and intra-chain charge transport in bulk polythiophene in the hopping regime has been clarified by studying the conductivity as a function of frequency (up to 3 THz), temperature and doping level. We present a model which quantitatively explains the observed crossover from quasi-one-dimensional transport to three-dimensional hopping conduction with increasing doping level. At high frequencies the conductivity is dominated by charge transport on one-dimensional conducting chains.
Equilibration of polymer melts containing highly entangled long polymer chains in confinement or with free surfaces is a challenge for computer simulations. We approach this problem by first studying polymer melts based on the soft-sphere coarse-grained model confined between two walls with periodic boundary conditions in two directions parallel to the walls. Then we apply backmapping to reinsert the microscopic details of the underlying bead-spring model. Tuning the strength of the wall potential, the monomer density of confined polymer melts in equilibrium is kept at the bulk density even ne…
The Kremer-Grest (KG) model is a standard for studying generic polymer properties. Here we have equilibrated KG melts up to and beyond $200$ entanglements per chain for varying chain stiffness. We present methods for estimating the Kuhn length corrected for incompressibility effects, for estimating the entanglement length corrected for chain stiffness, for estimating bead frictions and Kuhn times taking into account entanglement effects. These are the key parameters for enabling quantitative, accurate, and parameter free comparisons between theory, experiment and simulations of KG polymer mode…
The Kremer-Grest (KG) polymer model is a standard model for studying generic polymer properties in Molecular Dynamics simulations. It owes its popularity to its simplicity and computational efficiency, rather than its ability to represent specific polymers species and conditions. Here we show, that by tuning the chain stiffness it is possible to adapt the KG model to model melts of real polymers. In particular, we provide mapping relations from KG to SI units for a wide range of commodity polymers. The connection between the experimental and the KG melts is made at the Kuhn scale, i.e. at the …
We present the results from an extensive atomistic molecular dynamics simulation study of poly(ethylene oxide) (PEO) doped with various amounts of lithium-bis(trifluoromethane)sulfonimide (LiTFSI) salt under the influence of external electric field strengths up to $1\,$V/nm. The motivation stems from recent experimental reports on the nonlinear response of mobilities to the application of an electric field in such electrolyte systems and arising speculations on field-induced alignment of the polymer chains, creating channel-like structures that facilitate ion passage. Hence, we systematically …
We present a generalized theory for studying phase separation in blends of polymers containing dipoles on their backbone. The theory is used to construct co-existence curves and to study the effects of dipolar interactions on interfacial tension for a planar interface between the coexisting phases. We show that a mismatch in monomeric dipole moments, or equivalently a mismatch in the dielectric constant of the pure components, leads to destabilization of the homogeneous phase. Corrections to the Flory-Huggins phase diagram are predicted using the theory. Furthermore, we show that the interfaci…
The behavior of mesoscopic particles dissolved in a dilute solution of long, flexible, and nonadsorbing polymer chains is studied by field-theoretic methods. For spherical and cylindrical particles the solvation free energy for immersing a single particle in the solution is calculated explicitly. Important features are qualitatively different for self-avoiding polymer chains as compared with ideal chains. The results corroborate the validity of the Helfrich-type curvature expansion for general particle shapes and allow for quantitative experimental tests. For the effective interactions between…
Single polymer dynamics offers a powerful approach to study molecular-level interactions and dynamic microstructure in materials. Direct visualization of single chain dynamics has uncovered new ideas regarding the rheology and non-equilibrium dynamics of macromolecules, including the importance of molecular individualism, dynamic heterogeneity, and molecular sub-populations that govern macroscale behavior. In recent years, the field of single polymer dynamics has been extended to increasingly complex materials, including architecturally complex polymers such as combs, bottlebrushes, and ring p…
A brief review of modeling and simulation methods for a study of polymers at interfaces is provided. When studying truly multiscale problems as provided by realistic polymer systems, coarse graining is practically unavoidable. In this process, degrees of freedom on smaller scales are eliminated to the favor of a model suitable for efficient study of the system behavior on larger length and time scales. We emphasize the need to distinguish between dynamic and static properties regarding the model validation. A model which accurately reproduces static properties may fail completely, when it come…
Minimizing the elastic free energy of a thin sheet of nematic polymer network among smooth isometric immersions is the strategy purported by the mainstream theory. In this paper, we broaden the class of admissible spontaneous deformations: we consider ridged isometric immersions, which can cause a sharp ridge in the immersed surfaces. We propose a model to compute the extra energy distributed along such ridges. This energy comes from bending; it is shown under what circumstances it scales quadratically with the sheet's thickness, falling just in between stretching and bending energies. We put …
Field-theoretical method is efficient in predicting the assembling structures of polymeric systems. However, for the polymer/nanoparticle mixture, the continuous density description is not suitable to capture the realistic assembly of particles, especially when the size of particle is much larger than the polymer segment. Here, we developed a field-based model, in which the particles are eventually discrete and hence it can overcome the drawbacks of the conventional field descriptions, e.g., inadequate and crude treatment on the polymer-particle interface and the excluded-volume interaction. W…
Recent advances in nano-rheology require that new methods and models be developed to describe the equilibrium and non-equilibrium properties of entangled polymeric materials and their interfaces at a molecular level of detail. In this work we present a Slip-Spring (SLSP) model capable of describing the dynamics of entangled polymers at interfaces, including explicit liquid-vapor and liquid-solid interfaces. The highly coarse-grained approach adopted with this model enables simulation of entire nano-rheological characterization systems within a particle-level base description. Many-body dissipa…
Longstanding mechanistic questions about the role of protecting osmolyte trimethylamine N- oxide (TMAO) which favors protein folding and the denaturing osmolyte urea are addressed by studying their effects on the folding of uncharged polymer chains. Using atomistic molecular dynamics simulations, we show that 1-M TMAO and 7-M urea solutions act dramatically differently on these model polymer chains. Their behaviors are sensitive to the strength of the attractive dispersion interactions of the chain with its environment: when these dispersion interactions are high enough, TMAO suppresses the fo…
Polymer translocation through a nanometer-scale pore assisted by chaperones binding to the polymer is a process encountered in vivo for proteins. Studying the relevant models by computer simulations is computationally demanding. Accordingly, previous studies are either for stiff polymers in three dimensions or flexible polymers in two dimensions. Here, we study chaperone-assisted translocation of flexible polymers in three dimensions using Langevin dynamics. We show that differences in binding mechanisms, more specifically, whether a chaperone can bind to a single or multiple sites on the poly…
Hydrophobically modified polymers are good candidates for the stabilization of liquid interfaces thanks to the high anchoring energy of the hydrophobic parts. In this article we probe the interfacial anchoring of a series of home-made hydrophobically modified polymers of controlled degree of grafting by studying their behavior upon large area dilations and compressions. By comparing the measured interfacial tension to the one that we expect in the case of a constant number of adsorbed monomers, we are able to deduce whether desorption or adsorption occurs during area variations. We find that t…
In this work, we explore the dynamics of active entangled chains using molecular dynamics simulations of a modified Kremer-Grest model. The active chains are diluted in a mesh of very long passive linear chains, to avoid constraint release effects, and an active force is applied to the monomers in a way that it imparts a constant polar drift velocity along the primitive path. The simulation results show that, over a wide range of activity values, the conformational properties of the chains and the tubes are not affected, but the dynamics of the chains are severely modified. Despite not having …
Thin liquid films on surfaces are part of our everyday life, they serve e.g. as coatings or lubricants. The stability of a thin layer is governed by interfacial forces, described by the effective interface potential, and has been subject of many studies in the last decades. In recent years, the dynamics of thin liquid films came into focus since results on the reduction of the glass transition temperature raised new questions on the behavior of especially polymeric liquids in confined geometries. The new focus was fired by theoretical models that proposed significant implication of the boundar…
Single domain proteins are thought to be tightly packed. The introduction of voids by mutations is often regarded as destabilizing. In this study we show that packing density for single domain proteins decreases with chain length. We find that the radius of gyration provides poor description of protein packing but the alpha contact number we introduce here characterize proteins well. We further demonstrate that protein-like scaling relationship between packing density and chain length is observed in off-lattice self-avoiding walks. A key problem in studying compact chain polymer is the attriti…
We compare a newly developed hybrid simulation method which combines classical molecular dynamics (MD) and computational fluid dynamics (CFD) to a simulation consisting only of molecular dynamics. The hybrid code is composed of three regions: a classical MD region, a continuum domain where the dynamical equations are solved by standard CFD methods, and an overlap domain where transport information from the other two domains is exchanged. The exchange of information in the overlap region ensures that momentum, energy and mass are conserved. The validity of the hybrid code is demonstrated by stu…
The Rouse model can be regarded as the standard model to describe the dynamics of a short polymer chain under melt conditions. In this contribution, we explicitly check one of the fundamental assumptions of this model, namely that of a uniform friction coefficient for all monomers, on the basis of MD simulation data of a poly(ethylene oxide) (PEO) melt. This question immediately arises from the fact that in a real polymer melt the terminal monomers have on average more intermolecular neighbors than the central monomers, and one would expect that exactly these details affect the precise value o…
In studying the end-to-end distribution function $G(r,N)$ of a worm like chain by using the propagator method we have established that the combinatorial problem of counting the paths contributing to $G(r,N)$ can be mapped onto the problem of random walks with constraints, which is closely related to the representation theory of the Temperley-Lieb algebra. By using this mapping we derive an exact expression of the Fourier-Laplace transform of the distribution function, $G(k,p)$, as a matrix element of an inverse of an infinite rank matrix. Using this result we also derived a recursion relation …
We review various methods to investigate the statics and the dynamics of collective composition fluctuations in dense polymer mixtures within fluctuating-field approaches. The central idea of fluctuating-field theories is to rewrite the partition function of the interacting multi-chain systems in terms of integrals over auxiliary, often complex, fields, which are introduced by means of appropriate Hubbard-Stratonovich transformations. Thermodynamic averages like the average composition and the structure factor can be expressed exactly as averages of these fields. We discuss different analytica…
Polymer blends consisting of two or more polymers are important for a wide variety of industries and processes, but, the precise mechanism of their thermomechanical behaviour is incompletely understood. In order to understand clearly, it is essential to determine the miscibility and interactions between the components in polymer blend and its macroscopic thermomechanical properties. In this study, we performed experiments on SEBS and isotactic PP blends (SP) as well as molecular dynamics simulations, aiming to know the role played by molecular interactions on the thermomechanical properties. T…
The self-consistent field theory is a popular and highly successful theoretical framework for studying equilibrium (co)polymer systems at the mesoscopic level. Dynamic density functionals allow one to use this framework for studying dynamical processes in the diffusive, non-inertial regime. The central quantity in these approaches is the mobility function, which describes the effect of chain connectivity on the nonlocal response of monomers to thermodynamic driving fields. In a recent study [Mantha et al, Macromolecules 53, 3409 (2020)], we have developed a method to systematically construct m…
The transport of biomolecules across a cell membrane is an important phenomena that plays a pivotal role in the functioning of biological cells. In this paper, we investigate such processes by modeling the translocation of polymers through a conical channel, directed from the wider opening to the narrow end of the conical channel. We use the molecular dynamics approach to study the problem. The effect of the different conical pore geometry and polymer lengths on translocation dynamics is determined from the behavior of the total translocation time, $τ$, and waiting time distributions, $w(s)$. …
From Single-Chain Dynamics to Structure Formation: Dynamic Self-Consistent Field Theory and Molecular Dynamics of (Co)polymer Melts across Entanglement Regimes
Johannes Gutenberg-Universität Mainz（约翰内斯·古腾堡美因茨大学）
In this work, we present a simple and efficient generator of polymeric linear chains, based on a random self-avoiding walk process. The chains are generated using a discrete process of growth, in cubic networks and in a finite time, without border limits and without exploring all the configurational space. First, we thoroughly describe the chains morphology exploring the statistics of two characteristic distances, the radius of gyration and the end-to-end distance. Moreover, we examine the dependence of mean characteristic distances with the number of steps (N). Despite the simplicity of our p…
Dynamic density functionals (DDFs) are popular tools for studying the dynamical evolution of inhomogeneous polymer systems. Here, we present a systematic evaluation of a set of diffusive DDF theories by comparing their predictions with data from particle-based Brownian dynamics (BD) simulations for two selected problems: Interface broadening in compressible A/B homopolymer blends after a sudden change of the incompatibility parameter, and microphase separation in compressible A:B diblock copolymer melts. Specifically, we examine (i) a local dynamics model, where monomers are taken to move inde…
Spin coating is an out-of-equilibrium technique for producing polymer films and colloidal crystals quickly and reproducibly. In this review, we present an overview of theoretical and experimental studies of the spin coating of colloidal suspensions. The dynamics of the spin coating process is discussed first, and we present insights from both theory and experiment. A key difference between spin coating with polymer solutions and with monodisperse colloidal suspensions is the emergence of long range (centimeter scale) orientational correlations in the latter. We discuss experiments in different…
We consider a mesoscale model for nano-sized metaparticles (MPs) composed of a central sphere decorated by polymer chains with laterally attached spherocylinder. The latter mimics the mesogenic (e.g., cyanobiphenyl) group. Molecular dynamics simulations of $100$ MPs reveal the existence of two novel morphologies: $\textrm{uCol}_\mathrm{h}$ (hexagonal columnar arrangement of MPs with strong uniaxial order of mesogens collinear to the columns axis) and $\mathrm{wCol}_\mathrm{h}$ [the same arrangement of MPs but with weak or no liquid crystalline (LC) order]. Collinearity of the LC director and t…
