Collapsed 2-Dimensional Polymers on a Cylinder

Single partially confined collapsed polymers are studied in two dimensions. They are described by self-avoiding random walks with nearest-neighbour attractions below the $\Theta$-point, on the surface of an infinitely long cylinder. For the simulations we employ the pruned-enriched-Rosenbluth method (PERM). The same model had previously been studied for free polymers (infinite lattice, no boundaries) and for polymers on finite lattices with periodic boundary conditions. We verify the previous estimates of bulk densities, bulk free energies, and surface tensions. We find that the free energy of a polymer with fixed length $N$ has, for $N\to \infty$, a minimum at a finite cylinder radius $R^*$ which diverges as $T\to T_\theta$. Furthermore, the surface tension vanishes roughly as $(T_\theta-T)^\alpha$ for $T\to T_\theta$ with $\alpha\approx 1.7$. The density in the interior of a globule scales as $(T_\theta-T)^\beta$ with $\beta \approx 0.32$.Comment: 4 pages, 8 figure

First-order scaling near a second-order phase transition: Tricritical polymer collapse

The coil-globule transition of an isolated polymer has been well established to be a second-order phase transition described by a standard tricritical O(0) field theory. We provide compelling evidence from Monte Carlo simulations in four dimensions, where mean-field theory should apply, that the approach to this (tri)critical point is dominated by the build-up of first-order-like singularities masking the second-order nature of the coil-globule transition: the distribution of the internal energy having two clear peaks that become more distinct and sharp as the tricritical point is approached. However, the distance between the peaks slowly decays to zero. The evidence shows that the position of this (pseudo) first-order transition is shifted by an amount from the tricritical point that is asymptotically much larger than the width of the transition region. We suggest an explanation for the apparently contradictory scaling predictions in the literature.Comment: 4 pages, 2 figures included in tex

Phase Transitions of Single Semi-stiff Polymer Chains

We study numerically a lattice model of semiflexible homopolymers with nearest neighbor attraction and energetic preference for straight joints between bonded monomers. For this we use a new algorithm, the "Pruned-Enriched Rosenbluth Method" (PERM). It is very efficient both for relatively open configurations at high temperatures and for compact and frozen-in low-T states. This allows us to study in detail the phase diagram as a function of nn-attraction epsilon and stiffness x. It shows a theta-collapse line with a transition from open coils to molten compact globules (large epsilon) and a freezing transition toward a state with orientational global order (large stiffness x). Qualitatively this is similar to a recently studied mean field theory (Doniach et al. (1996), J. Chem. Phys. 105, 1601), but there are important differences. In contrast to the mean field theory, the theta-temperature increases with stiffness x. The freezing temperature increases even faster, and reaches the theta-line at a finite value of x. For even stiffer chains, the freezing transition takes place directly without the formation of an intermediate globule state. Although being in contrast with mean filed theory, the latter has been conjectured already by Doniach et al. on the basis of low statistics Monte Carlo simulations. Finally, we discuss the relevance of the present model as a very crude model for protein folding.Comment: 11 pages, Latex, 8 figure

Four-dimensional polymer collapse II: Pseudo-First-Order Transition in Interacting Self-avoiding Walks

In earlier work we provided the first evidence that the collapse, or coil-globule, transition of an isolated polymer in solution can be seen in a four-dimensional model. Here we investigate, via Monte Carlo simulations, the canonical lattice model of polymer collapse, namely interacting self-avoiding walks, to show that it not only has a distinct collapse transition at finite temperature but that for any finite polymer length this collapse has many characteristics of a rounded first-order phase transition. However, we also show that there exists a `$\theta$-point' where the polymer behaves in a simple Gaussian manner (which is a critical state), to which these finite-size transition temperatures approach as the polymer length is increased. The resolution of these seemingly incompatible conclusions involves the argument that the first-order-like rounded transition is scaled away in the thermodynamic limit to leave a mean-field second-order transition. Essentially this happens because the finite-size \emph{shift} of the transition is asymptotically much larger than the \emph{width} of the pseudo-transition and the latent heat decays to zero (algebraically) with polymer length. This scenario can be inferred from the application of the theory of Lifshitz, Grosberg and Khokhlov (based upon the framework of Lifshitz) to four dimensions: the conclusions of which were written down some time ago by Khokhlov. In fact it is precisely above the upper critical dimension, which is 3 for this problem, that the theory of Lifshitz may be quantitatively applicable to polymer collapse.Comment: 30 pages, 14 figures included in tex

Geometrical Properties of Two-Dimensional Interacting Self-Avoiding Walks at the Theta-Point

We perform a Monte Carlo simulation of two-dimensional N-step interacting self-avoiding walks at the theta point, with lengths up to N=3200. We compute the critical exponents, verifying the Coulomb-gas predictions, the theta-point temperature T_theta = 1.4986(11), and several invariant size ratios. Then, we focus on the geometrical features of the walks, computing the instantaneous shape ratios, the average asphericity, and the end-to-end distribution function. For the latter quantity, we verify in detail the theoretical predictions for its small- and large-distance behavior.Comment: 23 pages, 4 figure

Parallel Excluded Volume Tempering for Polymer Melts

We have developed a technique to accelerate the acquisition of effectively uncorrelated configurations for off-lattice models of dense polymer melts which makes use of both parallel tempering and large scale Monte Carlo moves. The method is based upon simulating a set of systems in parallel, each of which has a slightly different repulsive core potential, such that a thermodynamic path from full excluded volume to an ideal gas of random walks is generated. While each system is run with standard stochastic dynamics, resulting in an NVT ensemble, we implement the parallel tempering through stochastic swaps between the configurations of adjacent potentials, and the large scale Monte Carlo moves through attempted pivot and translation moves which reach a realistic acceptance probability as the limit of the ideal gas of random walks is approached. Compared to pure stochastic dynamics, this results in an increased efficiency even for a system of chains as short as $N = 60$ monomers, however at this chain length the large scale Monte Carlo moves were ineffective. For even longer chains the speedup becomes substantial, as observed from preliminary data for $N = 200$

Exact Enumeration Study of Free Energies of Interacting Polygons and Walks in Two Dimensions

We present analyses of substantially extended series for both interacting self-avoiding walks (ISAW) and polygons (ISAP) on the square lattice. We argue that these provide good evidence that the free energies of both linear and ring polymers are equal above the theta-temperature, extending the application of a theorem of Tesi et. al. to two dimensions. Below the $\theta$-temperature the conditions of this theorem break down, in contradistinction to three dimensions, but an analysis of the ratio of the partition functions for ISAP and ISAW indicates that the free energies are in fact equal at all temperatures to at least within 1%. Any perceived difference can be interpreted as the difference in the size of corrections-to-scaling in both problems. This may be used to explain the vastly different values of the cross-over exponent previously estimated for ISAP to that predicted theoretically, and numerically confirmed, for ISAW. An analysis of newly extended neighbour-avoiding SAW series is also given.Comment: 28 pages, 2 figure