Single chain properties of polyelectrolytes in poor solvent

Using molecular dynamics simulations we study the behavior of a dilute solution of strongly charged polyelectrolytes in poor solvents, where we take counterions explicitly into account. We focus on the chain conformational properties under conditions where chain-chain interactions can be neglected, but the counterion concentration remains finite. We investigate the conformations with regard to the parameters chain length, Coulomb interaction strength, and solvent quality, and explore in which regime the competition between short range hydrophobic interactions and long range Coulomb interactions leads to pearl-necklace like structures. We observe that large number and size fluctuations in the pearls and strings lead to only small direct signatures in experimental observables like the single chain form factor. Furthermore we do not observe the predicted first order collapse of the necklace into a globular structure when counterion condensation sets in. We will also show that the pearl-necklace regime is rather small for strongly charged polyelectrolytes at finite densities. Even small changes in the charge fraction of the chain can have a large impact on the conformation due to the delicate interplay between counterion distribution and chain conformation.Comment: 20 pages, 27 figures, needs jpc.sty (included), to appear in Jour. Phys. Chem

Geodesic boundary value problems with symmetry

This paper shows how left and right actions of Lie groups on a manifold may be used to complement one another in a variational reformulation of optimal control problems equivalently as geodesic boundary value problems with symmetry. We prove an equivalence theorem to this effect and illustrate it with several examples. In finite-dimensions, we discuss geodesic flows on the Lie groups SO(3) and SE(3) under the left and right actions of their respective Lie algebras. In an infinite-dimensional example, we discuss optimal large-deformation matching of one closed curve to another embedded in the same plane. In the curve-matching example, the manifold \Emb(S^1, \mathbb{R}^2) comprises the space of closed curves $S^1$ embedded in the plane $\mathbb{R}^2$. The diffeomorphic left action \Diff(\mathbb{R}^2) deforms the curve by a smooth invertible time-dependent transformation of the coordinate system in which it is embedded, while leaving the parameterisation of the curve invariant. The diffeomorphic right action \Diff(S^1) corresponds to a smooth invertible reparameterisation of the $S^1$ domain coordinates of the curve. As we show, this right action unlocks an important degree of freedom for geodesically matching the curve shapes using an equivalent fixed boundary value problem, without being constrained to match corresponding points along the template and target curves at the endpoint in time.Comment: First version -- comments welcome

Continuous and discrete Clebsch variational principles

The Clebsch method provides a unifying approach for deriving variational principles for continuous and discrete dynamical systems where elements of a vector space are used to control dynamics on the cotangent bundle of a Lie group \emph{via} a velocity map. This paper proves a reduction theorem which states that the canonical variables on the Lie group can be eliminated, if and only if the velocity map is a Lie algebra action, thereby producing the Euler-Poincar\'e (EP) equation for the vector space variables. In this case, the map from the canonical variables on the Lie group to the vector space is the standard momentum map defined using the diamond operator. We apply the Clebsch method in examples of the rotating rigid body and the incompressible Euler equations. Along the way, we explain how singular solutions of the EP equation for the diffeomorphism group (EPDiff) arise as momentum maps in the Clebsch approach. In the case of finite dimensional Lie groups, the Clebsch variational principle is discretised to produce a variational integrator for the dynamical system. We obtain a discrete map from which the variables on the cotangent bundle of a Lie group may be eliminated to produce a discrete EP equation for elements of the vector space. We give an integrator for the rotating rigid body as an example. We also briefly discuss how to discretise infinite-dimensional Clebsch systems, so as to produce conservative numerical methods for fluid dynamics

High precision single-cluster Monte Carlo measurement of the critical exponents of the classical 3D Heisenberg model

We report measurements of the critical exponents of the classical three-dimensional Heisenberg model on simple cubic lattices of size $L^3$ with $L$ = 12, 16, 20, 24, 32, 40, and 48. The data was obtained from a few long single-cluster Monte Carlo simulations near the phase transition. We compute high precision estimates of the critical coupling $K_c$, Binder's parameter $U^* and the critical exponents$\nu,\beta / \nu, \eta$, and$\alpha / \nu$, using extensively histogram reweighting and optimization techniques that allow us to keep control over the statistical errors. Measurements of the autocorrelation time show the expected reduction of critical slowing down at the phase transition as compared to local update algorithms. This allows simulations on significantly larger lattices than in previous studies and consequently a better control over systematic errors in finite-size scaling analyses.Comment: 4 pages, (contribution to the Lattice92 proceedings) 1 postscript file as uufile included. Preprints FUB-HEP 21/92 and HLRZ 89/92. (note: first version arrived incomplete due to mailer problems

How Close to Two Dimensions Does a Lennard-Jones System Need to Be to Produce a Hexatic Phase?

We report on a computer simulation study of a Lennard-Jones liquid confined in a narrow slit pore with tunable attractive walls. In order to investigate how freezing in this system occurs, we perform an analysis using different order parameters. Although some of the parameters indicate that the system goes through a hexatic phase, other parameters do not. This shows that to be certain whether a system has a hexatic phase, one needs to study not only a large system, but also several order parameters to check all necessary properties. We find that the Binder cumulant is the most reliable one to prove the existence of a hexatic phase. We observe an intermediate hexatic phase only in a monolayer of particles confined such that the fluctuations in the positions perpendicular to the walls are less then 0.15 particle diameters, i. e. if the system is practically perfectly 2d

Finite Size Polyelectrolyte Bundles at Thermodynamic Equilibrium

We present the results of extensive computer simulations performed on solutions of monodisperse charged rod-like polyelectrolytes in the presence of trivalent counterions. To overcome energy barriers we used a combination of parallel tempering and hybrid Monte Carlo techniques. Our results show that for small values of the electrostatic interaction the solution mostly consists of dispersed single rods. The potential of mean force between the polyelectrolyte monomers yields an attractive interaction at short distances. For a range of larger values of the Bjerrum length, we find finite size polyelectrolyte bundles at thermodynamic equilibrium. Further increase of the Bjerrum length eventually leads to phase separation and precipitation. We discuss the origin of the observed thermodynamic stability of the finite size aggregates