arXiv subjects

C. N. Likos

Publications and source records attributed to C. N. Likos.

At least 19 recordsLinked to original sources

arXiv2019

Hydrodynamic Inflation of Ring Polymers under Shear

Hydrodynamic interactions as modeled by Multi-Particle Collision Dynamics can dramatically influence the dynamics of fully flexible, ring-shaped polymers in ways not known for any other polymer architecture or topology. We show that steady shear leads to an inflation scenario exclusive to ring polymers, which depends not only on Weissenberg number but also on contour length of the ring. By analyzing velocity fields of the solvent around the polymer, we show the existence of a hydrodynamic pocket which allows the polymer to self-stabilize at a certain alignment angle to the flow axis. This self-induced stabilization is accompanied by transitioning of the ring to a non-Brownian particle and a cessation of tumbling. The ring swells significantly in the vorticity direction, and the horseshoe regions on the stretched and swollen ring are effectively locked in place relative to the ring's center-of-mass. The observed effect is exclusive to ring polymers and stems from an interplay between hydrodynamic interactions and topology. Furthermore, knots tied onto such rings can serve as additional "stabilization anchors". Under strong shear, the knotted section is pulled tight and remains well-localized while tank-treading from one horseshoe region to the opposite one in sudden bursts. We find knotted polymers of high contour length behave very similarly to unknotted rings of the same contour length, but small knotted rings feature a host of different configurations. We propose a filtering technique for rings and chains based on our observations and suggest that strong shear could be used to tighten knots on rings.

cond-mat.soft↗

arXiv2013

Controlling the Interactions between Soft Colloids via Surface Adsorption

By employing monomer-resolved computer simulations and analytical considerations based on polymer scaling theory, we analyze the conformations and interactions of multiarm star polymers strongly adsorbed on a smooth, two-dimensional plane. We find a stronger stretching of the arms as well as a stronger repulsive, effective interaction than in the three dimensional case. In particular, the star size scales with the number of arms $f$ as $\sim f^{1/4}$ and the effective interaction as $\sim f^{2}$, as opposed to $\sim f^{1/5}$ and $\sim f^{3/2}$, respectively, in three dimensions. Our results demonstrate the dramatic effect that geometric confinement can have on the effective interactions and the subsequent correlations of soft colloids in general, for which the conformation can be altered as a result of geometrical constraints imposed on them.

cond-mat.soft↗

arXiv2010

Tailoring the Phonon Band Structure in Binary Colloidal Mixtures

We analyze the phonon spectra of periodic structures formed by two-dimensional mixtures of dipolar colloidal particles. These mixtures display an enormous variety of complex ordered configurations [J. Fornleitner {\it et al.}, Soft Matter {\bf 4}, 480 (2008)], allowing for the systematic investigation of the ensuing phonon spectra and the control of phononic gaps. We show how the shape of the phonon bands and the number and width of the phonon gaps can be controlled by changing the susceptibility ratio, the concentration and the mass ratio between the two components.

cond-mat.soft↗

arXiv2007

Long-time self-diffusion of Brownian Gaussian-core particles

Using extensive Brownian dynamics computer simulations, the long-time self-diffusion coefficient is calculated for Gaussian-core particles as a function of the number density. Both spherical and rod-like particles interacting via Gaussian segments ar$ For increasing concentration we find that the translational self-diffusion behaves non-monotonically reflecting the structural reentrance effect in the equilibrium phase diagram. Both in the limits of zero and infinite concentration, it approaches its short-time value. The microscopic Medina-Noyola theory qualitatively accounts for the translational long-time diffusion. The long-time orientational diffusion coefficient for Gaussian rods, on the other hand, remains very close to its short-time counterpart for any density. Some implications of the weak translation-rotation coupling for ultrasoft rods are discussed.

cond-mat.soft↗

arXiv2006

Fluid-fluid demixing transitions in colloid--polyelectrolyte star mixtures

We derive effective interaction potentials between hard, spherical colloidal particles and star-branched polyelectrolytes of various functionalities and smaller size than the colloids. The effective interactions are based on a Derjaguin-like approximation, which is based on previously derived potentials acting between polyelectrolyte stars and planar walls. On the basis of these interactions we subsequently calculate the demixing binodals of the binary colloid--polyelectrolyte star mixture, employing standard tools from liquid-state theory. We find that the mixture is indeed unstable at moderately high overall concentrations. The system becomes more unstable with respect to demixing as the star functionality and the size ratio grow.

cond-mat.soft↗

arXiv2005

Structure, phase behavior and inhomogeneous fluid properties of binary dendrimer mixtures

The effective pair potentials between different kinds of dendrimers in solution can be well approximated by appropriate Gaussian functions. We find that in binary dendrimer mixtures the range and strength of the effective interactions depend strongly upon the specific dendrimer architecture. We consider two different types of dendrimer mixtures, employing the Gaussian effective pair potentials, to determine the bulk fluid structure and phase behavior. Using a simple mean field density functional theory (DFT) we find good agreement between theory and simulation results for the bulk fluid structure. Depending on the mixture, we find bulk fluid-fluid phase separation (macro-phase separation) or micro-phase separation, i.e., a transition to a state characterized by undamped periodic concentration fluctuations. We also determine the inhomogeneous fluid structure for confinement in spherical cavities. Again, we find good agreement between the DFT and simulation results. For the dendrimer mixture exhibiting micro-phase separation, we observe rather striking pattern formation under confinement.

cond-mat.soft↗

arXiv2005

Tailoring the flow of soft glasses by soft additives

We examine the vitrification and melting of asymmetric star polymers mixtures by combining rheological measurements with mode coupling theory. We identify two types of glassy states, a {\it single} glass, in which the small component is fluid in the glassy matrix of the big one and a {\it double} glass, in which both components are vitrified. Addition of small star polymers leads to melting of {\it both} glasses and the melting curve has a non-monotonic dependence on the star-star size ratio. The phenomenon opens new ways for externally steering the rheological behavior of soft matter systems.

cond-mat.soft↗

arXiv2005

Accurate description of bulk and interfacial properties in colloid-polymer mixtures

Large-scale Monte Carlo simulations of a phase-separating colloid-polymer mixture are performed and compared to recent experiments. The approach is based on effective interaction potentials in which the central monomers of self-avoiding polymer chains are used as effective coordinates. By incorporating polymer nonideality together with soft colloid-polymer repulsion, the predicted binodal is in excellent agreement with recent experiments. In addition, the interfacial tension as well as the capillary length are in quantitative agreement with experimental results obtained at a number of points in the phase-coexistence region, without the use of any fit parameters

cond-mat.soft↗

arXiv2004

Microscopic and coarse-grained correlation functions in concentrated dendrimer solutions

We employ monomer-resolved computer simulations of model dendrimer molecules, to examine the significance of many-body effects in concentrated solutions of the same. In particular, we measure the radial distribution functions and the scattering functions between the centres of mass of the dissolved dendrimers at various concentrations, reaching values that slightly exceed the overlap density of the macromolecules. We analyse the role played by many-body effective interactions by comparing the structural data to those obtained by applying exclusively the previously obtained two-body effective interactions between the dendrimers [G{ö}tze I O, Harreis H M and Likos C N 2004 {\it J. Chem. Phys.} {\bf 120} 7761]. We find that the effects of the many-body forces are small in general and they become weaker as the dendrimer flexibility increases. Moreover, we test the validity of the oft-used factorisation approximation to the total scattering intensity into a product of the form- and the scattering factors, finding a breakdown of this factorisation at high concentrations.

cond-mat.soft↗

arXiv2004

Is there a reentrant glass in binary mixtures?

By employing computer simulations for a model binary mixture, we show that a reentrant glass transition upon adding a second component only occurs if the ratio $α$ of the short-time mobilities between the glass-forming component and the additive is sufficiently small. For $α\approx 1$, there is no reentrant glass, even if the size asymmetry between the two components is large, in accordance with two-component mode coupling theory. For $α\ll 1$, on the other hand, the reentrant glass is observed and reproduced only by an effective one-component mode coupling theory.

cond-mat.soft↗

arXiv2003

Depletion forces in non-equilibrium

The concept of effective depletion forces between two fixed big colloidal particles in a bath of small particles is generalized to a non-equilibrium situation where the bath of small Brownian particles is flowing around the big particles with a prescribed velocity. In striking contrast to the equilibrium case, the non-equilibrium forces violate Newton's third law, are non-conservative and strongly anisotropic, featuring both strong attractive and repulsive domains.

cond-mat.soft↗

arXiv2003

Structural arrest in dense star polymer solutions

The dynamics of star polymers has been investigated via extensive Molecular- and Brownian Dynamics simulations for a large range of functionality $f$ and packing fraction $η$. The calculated isodiffusivity curves display both minima and maxima as a function of $η$ and minima as a function of $f$. Simulation results are compared with theoretical predictions based on different approximations for the structure factor. In particular, the ideal glass transition line predicted by mode-coupling theory is shown to exactly track the isodiffusivity curves, offering a theoretical understanding for the observation of disordered arrested states in star polymer solutions.

cond-mat.soft↗

arXiv2003

Mean-field dynamical density functional theory

We examine the out-of-equilibrium dynamical evolution of density profiles of ultrasoft particles under time-varying external confining potentials in three spatial dimensions. The theoretical formalism employed is the dynamical density functional theory (DDFT) of Marini Bettolo Marconi and Tarazona [J. Chem. Phys. {\bf 110}, 8032 (1999)], supplied by an equilibrium excess free energy functional that is essentially exact. We complement our theoretical analysis by carrying out extensive Brownian Dynamics simulations. We find excellent agreement between theory and simulations for the whole time evolution of density profiles, demonstrating thereby the validity of the DDFT when an accurate equilibrium free energy functional is employed.

cond-mat.soft↗

arXiv2001

Phase Behavior of Columnar DNA Assemblies

The pair interaction between two stiff parallel linear DNA molecules depends not only on the distance between their axes but on their azimuthal orientation. The positional and orientational order in columnar B-DNA assemblies in solution is investigated, based on the DNA-DNA electrostatic pair potential that takes into account DNA helical symmetry and the amount and distribution of adsorbed counterions. A phase diagram obtained by lattice sum calculations predicts a variety of positionally and azimuthally ordered phases and bundling transitions strongly depending on the counterion adsorption patterns.

cond-mat.soft↗

arXiv2001

Sedimentation profiles of systems with reentrant melting behavior

We examine sedimentation density profiles of star polymer solutions as an example of colloidal systems in sedimentation equilibrium which exhibit reentrant melting in their bulk phase diagram. Phase transitions between a fluid and a fluid with an intercalated solid are observed below a critical gravitational strength $α^{*}$. Characteristics of the two fluid-solid interfaces in the density profiles occurring in Monte Carlo simulations for $α< α^{*}$ are in agreement with scaling laws put forth in the framework of a phenomenological theory. Furthermore we detect density oscillations at the fluid-gas interface at high altitudes for high gravitational fields, which are verified with density functional theory and should be observable in surface scattering experiments.

cond-mat.soft↗

arXiv2000

Effective interactions between star polymers and colloidal particles

Using monomer-resolved Molecular Dynamics simulations and theoretical arguments based on the radial dependence of the osmotic pressure in the interior of a star, we systematically investigate the effective interactions between hard, colloidal particles and star polymers in a good solvent. The relevant parameters are the size ratio q between the stars and the colloids, as well as the number of polymeric arms f (functionality) attached to the common center of the star. By covering a wide range of q's ranging from zero (star against a flat wall) up to about 0.75, we establish analytical forms for the star-colloid interaction which are in excellent agreement with simulation results. A modified expression for the star-star interaction for low functionalities, f < 10 is also introduced.

cond-mat.soft↗

arXiv2000

Soft Interaction Between Dissolved Dendrimers: Theory and Experiment

Using small-angle neutron scattering and liquid integral equation theory, we relate the structure factor of flexible dendrimers of 4th generation to their average shape. The shape is measured as a radial density profile of monomers belonging to a single dendrimer. From that, we derive an effective interaction of Gaussian form between pairs of dendrimers and compute the structure factor using the hypernetted chain approximation. Excellent agreement with the corresponding experimental results is obtained, without the use of adjustable parameters. The present analysis thus strongly supports the previous finding that flexible dendrimers of low generation present fluctuating structures akin to star polymers.

cond-mat.soft↗

arXiv2000

Exact Criterion for Determining Clustering vs. Reentrant Melting Behavior for Bounded Interaction Potentials

We examine in full generality the phase behavior of systems whose constituent particles interact by means of potentials which do not diverge at the origin, are free of attractive parts and decay fast enough to zero as the interparticle separation r goes to infinity. By employing a mean field-density functional theory which is shown to become exact at high temperatures and/or densities, we establish a criterion which determines whether a given system will freeze at all temperatures or it will display reentrant melting and an upper freezing temperature.

cond-mat.soft↗