Four-dimensional polymer collapse: pseudo-first-order transition in interacting self-avoiding walks

Abstract

In an 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 "straight 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 shift of the transition is asymptotically much larger than the width of the pseudotransition 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.