arXiv subjects

Shuanhu Qi

Publications and source records attributed to Shuanhu Qi.

13 recordsLinked to original sources

arXiv2020

Bottom-up construction of dynamic density functional theories for inhomogeneous polymer systems from microscopic simulations

We propose and compare different strategies to construct dynamic density functional theories (DDFTs) for inhomogeneous polymer systems close to equilibrium from microscopic simulation trajectories. We focus on the systematic construction of the mobility coefficient, $Λ(r,r')$, which relates the thermodynamic driving force on monomers at position $r'$ to the motion of monomers at position $r$. A first approach based on the Green-Kubo formalism turns out to be impractical because of a severe plateau problem. Instead, we propose to extract the mobility coefficient from an effective characteristic relaxation time of the single chain dynamic structure factor. To test our approach, we study the kinetics of ordering and disordering in diblock copolymer melts. The DDFT results are in very good agreement with the data from corresponding fine-grained simulations.

cond-mat.soft↗

arXiv2019

How ill-defined constituents produce well-defined nanoparticles: Effect of polymer dispersity on the uniformity of copolymeric micelles

We investigate the effect of polymer length dispersity on the properties of self-assembled micelles in solution by self-consistent field calculations. Polydispersity stabilizes micelles by raising the free energy barriers of micelle formation and dissolution. Most importantly, it significantly reduces the size fluctuations of micelles: Block copolymers of moderate polydispersity form more uniform particles than their monodisperse counterparts. We attribute this to the fact that the packing of the solvophobic monomers in the core can be optimized if the constituent polymers have different length.

cond-mat.soft↗

arXiv2018

Anomalous Critical Slowdown at a First Order Phase Transition in Single Polymer Chains

Using Brownian Dynamics, we study the dynamical behavior of a polymer grafted onto an adhesive surface close to the mechanically induced adsorption-stretching transition. Even though the transition is first order, (in the infinite chain length limit, the stretching degree of the chain jumps discontinuously), the characteristic relaxation time is found to grow according to a power law as the transition point is approached. We present a dynamic effective interface model which reproduces these observations and provides an excellent quantitaive description of the simulations data. The generic nature of the theoretical model suggests that the unconventional mixing of features that are characteristic for first-order transitions (a jump in an order parameter) and features that are characteristic of critical points (anomalous slowdown) may be a common phenomenon in force-driven phase transitions of macromolecules.

cond-mat.soft↗

arXiv2018

Phase transitions in single macromolecules: loop-stretch transition versus loop adsorption transition in end-grafted polymer chains

We use Brownian dynamics simulations and analytical theory to compare two prominent types of single molecule transitions. One is the adsorption transition of a loop (a chain with two ends bound to an attractive substrate) driven by an attraction parameter $\varepsilon$, and the other is the loop-stretch transition in a chain with one end attached to a repulsive substrate, driven by an external end-force $F$ applied to the free end. Specifically, we compare the behavior of the respective order parameters of the transitions, i.e., the mean number of surface contacts in the case of the adsorption transition, and the mean position of the chain end in the case of the loop-stretch transition. Close to the transition points, both the static and the dynamic behavior of chains with different length $N$ are very well described by a scaling Ansatz with the scaling parameters $(\varepsilon - \varepsilon^*) N^ϕ$ (adsorption transition) and $(F-F^*) N^ν$ (loop-stretch transition), respectively, where $ϕ$ is the crossover exponent of the adsorption transition, and $ν$ the Flory exponent. We show that both the loop-stretch and the loop adsorption transitions provide an exceptional opportunity to construct explicit analytical expressions for the crossover functions which perfectly describe all simulation results on static properties in the finite-size scaling regime. Explicit crossover functions are based on the Ansatz for the analytical form of the order parameter distributions at the respective transition points. In contrast to the close similarity in equilibrium static behavior, the dynamic relaxation at the two transitions shows qualitative differences, especially in the strongly ordered regimes.

cond-mat.soft↗

arXiv2017

Dynamic density functional theories for inhomogeneous polymer systems compared to Brownian dynamics simulations

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 independently from each other, (ii) a nonlocal "chain dynamics" model, where monomers move jointly with correlation matrix given by the local chain correlator, and (iii,iv) two popular approximations to (ii), namely (iii) the Debye dynamics model, where the chain correlator is approximated by its value in a homogeneous system, and (iv) the computationally efficient "external potential dynamics" (EPD) model. With the exception of EPD, the value of the compressibility parameter has little influence on the results. In the interface broadening problem, the chain dynamics model reproduces the BD data best. However, the closely related EPD model produces large spurious artefacts. These artefacts disappear when the blend system becomes incompressible. In the microphase separation problem, the predictions of the nonlocal models (ii-iv) agree with each other and significantly overestimate the ordering time, whereas the local model (i) underestimates it. We attribute this to the multiscale character of the ordering process, which involves both local and global chain rearrangements. To account for this, we propose a mixed local/nonlocal DDF scheme which quantitatively reproduces all BD simulation data considered here.

cond-mat.soft↗

arXiv2017

Hybrid Particle-Continuum Simulations Coupling Brownian Dynamics and Local Dynamic Density Functional Theory

We present a multiscale hybrid particle-field scheme for the simulation of relaxation and diffusion behavior of soft condensed matter systems. It combines particle-based Brownian dynamics and field-based local dynamics in an adaptive sense such that particles can switch their level of resolution on the fly. The switching of resolution is controlled by a tuning function which can be chosen at will according to the geometry of the system. As an application, the hybrid scheme is used to study the kinetics of interfacial broadening of a polymer blend, and is validated by comparing the results to the predictions from pure Brownian dynamics and pure local dynamics calculations.

cond-mat.soft↗

arXiv2016

Polydisperse polymer brushes: internal structure, critical behavior, and interaction with flow

We study the effect of polydispersity on the structure of polymer brushes by analytical theory, a numerical self-consistent field approach, and Monte Carlo simulations. The polydispersity is represented by the Schulz-Zimm chain-length distribution. We specifically focus on three different polydispersities representing sharp, moderate and extremely wide chain length distributions and derive explicit analytical expressions for the chain end distributions in these brushes. The results are in very good agreement with numerical data obtained with self-consistent field calculations and Monte Carlo simulations. With increasing polydispersity, the brush density profile changes from convex to concave, and for given average chain length $N_n$ and grafting density $σ$, the brush height $H$ is found to scale as $(H/H_{\mathrm{mono}}-1)\propto(N_w/N_n-1)^{1/2}$ over a wide range of polydispersity indices $N_w/N_n$ (here $H_{\mathrm{mono}}$ is the height of the corresponding monodisperse brush. Chain end fluctuations are found to be strongly suppressed already at very small polydispersity. Based on this observation, we introduce the concept of the brush as a near-critical system with two parameters (scaling variables), $(N_{n}σ^{2/3})^{-1}$ and $(N_w/N_n-1)^{1/2}$, controlling the distance from the critical point. This approach provides a good description of the simulation data. Finally we study the hydrodynamic penetration length $l_\mathrm{p}$ for brush-coated surfaces in flow. We find that it generally increases with polydispersity. The scaling behavior crosses over from $l_\mathrm{p}\sim N_\mathrm{n}^{1/2}σ^{-1/6}$ for monodisperse and weakly polydisperse brushes to $l_\mathrm{p}\sim N_{n}^{2/3}$ for strongly polydisperse brushes.

cond-mat.soft↗

arXiv2016

A hybrid particle-continuum resolution method and its application to a homopolymer solution

We discuss in detail a recently proposed hybrid particle-continuum scheme for complex fluids and evaluate it at the example of a confined homopolymer solution in slit geometry. The hybrid scheme treats polymer chains near the impenetrable walls as particles keeping the configuration details, and chains in the bulk region as continuous density fields. Polymers can switch resolutions on the fly, controlled by an inhomogeneous tuning function. By properly choosing the tuning function, the representation of the system can be adjusted to reach an optimal balance between physical accuracy and computational efficiency. The hybrid simulation reproduces the results of a reference particle simulation and is significantly faster (about a factor of 3.5 in our application example).

cond-mat.soft↗

arXiv2015

Stimuli-responsive brushes with active minority components: Monte Carlo study and analytical theory

Using a combination of analytical theory, Monte Carlo simulations, and three dimensional self-consistent field calculations, we study the equilibrium properties and the switching behavior of adsorption-active polymer chains included in a homopolymer brush. The switching transition is driven by a conformational change of a small fraction of minority chains, which are attracted by the substrate. Depending on the strength of the attractive interaction, the minority chains assume one of two states: An exposed state characterized by a stem-crown-like conformation, and an adsorbed state characterized by a flat two-dimensional structure. Comparing the Monte Carlo simulations, which use an Edwards-type Hamiltonian with density dependent interactions, with the predictions from self-consistent-field theory based on the same Hamiltonian, we find that thermal density fluctuations affect the system in two different ways. First, they renormalize the excluded volume interaction parameter $v_\mathrm{\tiny bare}$ inside the brush. The properties of the brushes can be reproduced by self-consistent field theory if one replaces $v_\mathrm{\tiny bare}$ by an effective parameter $v_{\mathrm{\tiny eff}}$, where the ratio of second virial coefficients $B_{\mathrm{\tiny eff}}/B_\mathrm{\tiny bare}$ depends on the range of monomer interactions, but not on the grafting density, the chain length, and $v_\mathrm{\tiny bare}$. Second, density fluctuations affect the conformations of chains at the brush surface and have a favorable effect on the characteristics of the switching transition: In the interesting regime where the transition is sharp, they reduce the free energy barrier between the two states significantly. The scaling behavior of various quantities is also analyzed and compared with analytical predictions.

cond-mat.soft↗

arXiv2014

Sharp and fast: Sensors and switches based on polymer brushes with adsorption-active minority chains

We propose a design for polymer-based sensors and switches with sharp switching transition and fast response time. The switching mechanism involves a radical change in the conformations of adsorption-active minority chains in a brush. Such transitions can be induced by a temperature change of only about ten degrees, and the characteristic time of the conformational change is less than a second. We present an analytical theory for these switches and support it by self-consistent field calculations and Brownian dynamics simulations.

cond-mat.soft↗

arXiv2013

Using field theory to construct hybrid particle-continuum simulation schemes with adaptive resolution for soft matter systems

We develop a multiscale hybrid scheme for simulations of soft condensed matter systems, which allows one to treat the system at the particle level in selected regions of space, and at the continuum level elsewhere. It is derived systematically from an underlying particle-based model by field theoretic methods. Particles in different representation regions can switch representations on the fly, controlled by a spatially varying tuning function. As a test case, the hybrid scheme is applied to simulate colloid-polymer composites with high resolution regions close to the colloids. The hybrid simulations are significantly faster than reference simulations of a pure particle-based model, and the results are in good agreement.

cond-mat.soft↗

arXiv2009

Contour-Variable Model of Constitutive Equations for Polymer Melts

Based on a modified expression of the rate of the convective constraint release, we present a new contour-variable model of constitutive equations in which the non-uniform segmental stretch and the non-Gaussian chain statistical treatment of the single chain are considered to describe the polymer chain dynamics and the rheological behavior of an entangled system composed of linear polymer chains. The constitutive equations are solved numerically in the cases of steady shear and transient start-up of steady shear. The results indicate that the orientation and stretch, as well as the tube survival probability, have strong dependence on the chain contour variable, especially in the high-shear-rate region. However, the inclusion of the non-uniform features in the constitutive models has little modification comparing with the uniform models in determining the rheological properties both qualitatively and quantitatively.

physics.flu-dyn↗

arXiv2009

An external potential dynamic study on the formation of interface in polydisperse polymer blends

The formation of interface from an initial sharp interface in polydisperse A/B blends is studied using the external potential dynamic method. The present model is a nonlocal coupling model as we take into account the correlation between segments in a single chain. The correlation is approximately expressed by Debye function and the diffusion dynamics are based on the Rouse chain model. The chain length distribution is described by the continuous Schulz distribution. Our numerical calculation indicates that the broadening of interface with respect to time obeys a power law at early times, and the power law indexes are the same for both monodisperse and polydisperse blend. The power law index is larger than that in the local coupling model. However there is not a unified scaling form of the broadening of the interface width if only the interfacial width at equilibrium is taken into account as the characteristic length of the system, because the correlation makes an extra characteristic length in the system, and the polydispersity is related to this length.

cond-mat.soft↗