Individual Entanglements in a Simulated Polymer Melt

We examine entanglements using monomer contacts between pairs of chains in a Brownian-dynamics simulation of a polymer melt. A map of contact positions with respect to the contacting monomer numbers (i,j) shows clustering in small regions of (i,j) which persists in time, as expected for entanglements. Using the ``space''-time correlation function of the aforementioned contacts, we show that a pair of entangled chains exhibits a qualitatively different behavior than a pair of distant chains when brought together. Quantitatively, about 50% of the contacts between entangled chains are persistent contacts not present in independently moving chains. In addition, we account for several observed scaling properties of the contact correlation function.Comment: latex, 12 pages, 7 figures, postscript file available at http://arnold.uchicago.edu/~ebn

Renormalization of the one-loop theory of fluctuations in polymer blends and diblock copolymer melts

Attempts to use coarse-grained molecular theories to calculate corrections to the random-phase approximation (RPA) for correlations in polymer mixtures have been plagued by an unwanted sensitivity to the value of an arbitrary cutoff length, {\it i.e.}, by an ultraviolet (UV) divergence. We analyze the UV divergence of the inverse structure factor $S^{-1}(k)$ predicted by a `one-loop' approximation similar to that used in several previous studies. We consider both miscible homopolymer blends and disordered diblock copolymer melts. We show, in both cases, that all UV divergent contributions can be absorbed into a renormalization of the values of the phenomenological parameters of a generalized self-consistent field theory (SCFT). This observation allows the construction of a UV convergent theory of corrections to SCFT phenomenology. The UV-divergent one-loop contribution to $S^{-1}(k)$ are shown to be the sum of: (i) a $k$-independent contribution that arises from a renormalization of the effective $\chi$ parameter, (ii) a $k$-dependent contribution that arises from a renormalization of monomer statistical segment lengths, (iii) a contribution proportional to $k^{2}$ that arises from a square-gradient contribution to the one-loop fluctuation free energy, and (iv) a $k$-dependent contribution that is inversely proportional to the degree of polymerization, which arises from local perturbations in fluid structure near chain ends and near junctions between blocks in block copolymers.Comment: 35 pages, 2 figure

Unusual metallic phase in a chain of strongly interacting particles

We consider a one-dimensional lattice model with the nearest-neighbor interaction $V_1$ and the next-nearest neighbor interaction $V_2$ with filling factor 1/2 at zero temperature. The particles are assumed to be spinless fermions or hard-core bosons. Using very simple assumptions we are able to predict the basic structure of the insulator-metal phase diagram for this model. Computations of the flux sensitivity support the main features of the proposed diagram and show that the system maintains metallic properties at arbitrarily large values of $V_1$ and $V_2$ along the line $V_1-2V_2=\gamma J$, where $J$ is the hopping amplitude, and $\gamma\approx1.2$. We think that close to this line the system is a ``weak'' metal in a sense that the flux sensitivity decreases with the size of the system not exponentially but as $1/L^\alpha$ with $\alpha>1$.Comment: To appear in J. Phys. C; 9 revtex preprint pages + 4 ps figures, uuencode

Renormalized one-loop theory of correlations in polymer blends

The renormalized one-loop theory is a coarse-grained theory of corrections to the self-consistent field theory (SCFT) of polymer liquids, and to the random phase approximation (RPA) theory of composition fluctuations. We present predictions of corrections to the RPA for the structure function $S(k)$ and to the random walk model of single-chain statics in binary homopolymer blends. We consider an apparent interaction parameter $\chi_{a}$ that is defined by applying the RPA to the small $k$ limit of $S(k)$. The predicted deviation of $\chi_{a}$ from its long chain limit is proportional to $N^{-1/2}$, where $N$ is chain length. This deviation is positive (i.e., destabilizing) for weakly non-ideal mixtures, with \chi_{a} N \alt 1, but negative (stabilizing) near the critical point. The positive correction to $\chi_{a}$ for low values of $\chi_{a} N$ is a result of the fact that monomers in mixtures of shorter chains are slightly less strongly shielded from intermolecular contacts. The depression in $\chi_{a}$ near the critical point is a result of long-wavelength composition fluctuations. The one-loop theory predicts a shift in the critical temperature of ${\cal O}(N^{-1/2})$, which is much greater than the predicted ${\cal O}(N^{-1})$ width of the Ginzburg region. Chain dimensions deviate slightly from those of a random walk even in a one-component melt, and contract slightly with increasing $\chi_{e}$. Predictions for $S(k)$ and single-chain properties are compared to published lattice Monte Carlo simulations.Comment: submitted to J. Chem. Phy

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

Adsorption transition of a self-avoiding polymer chain onto a rigid rod

The subject of this work is the adsorption transition of a long flexible self-avoiding polymer chain onto a rigid thin rod. The rod is represented by a cylinder of radius R with a short-ranged attractive surface potential for the chain monomers. General scaling results are obtained by using renormalization group arguments in conjunction with available results for quantum field theories with curved boundaries [McAvity and Osborn 1993 Nucl. Phys. B 394, 728]. Relevant critical exponents are identified and estimated using geometric arguments.Comment: 19 pages, 4 figures. To appear in: J. Phys.: Condens. Matter, special issue dedicated to Lothar Schaefer on the occasion of his 60th birthda

Consistent coarse-graining strategy for polymer solutions in the thermal crossover from Good to Theta solvent

We extend our previously developed coarse-graining strategy for linear polymers with a tunable number n of effective atoms (blobs) per chain [D'Adamo et al., J. Chem. Phys. 137, 4901 (2012)] to polymer systems in thermal crossover between the good-solvent and the Theta regimes. We consider the thermal crossover in the region in which tricritical effects can be neglected, i.e. not too close to the Theta point, for a wide range of chain volume fractions Phi=c/c* (c* is the overlap concentration), up to Phi=30. Scaling crossover functions for global properties of the solution are obtained by Monte-Carlo simulations of the Domb-Joyce model. They provide the input data to develop a minimal coarse-grained model with four blobs per chain. As in the good-solvent case, the coarse-grained model potentials are derived at zero density, thus avoiding the inconsistencies related to the use of state-dependent potentials. We find that the coarse-grained model reproduces the properties of the underlying system up to some reduced density which increases when lowering the temperature towards the Theta state. Close to the lower-temperature crossover boundary, the tetramer model is accurate at least up to Phi<10, while near the good-solvent regime reasonably accurate results are obtained up to Phi<2. The density region in which the coarse-grained model is predictive can be enlarged by developing coarse-grained models with more blobs per chain. We extend the strategy used in the good-solvent case to the crossover regime. This requires a proper treatment of the length rescalings as before, but also a proper temperature redefinition as the number of blobs is increased. The case n=10 is investigated. Comparison with full-monomer results shows that the density region in which accurate predictions can be obtained is significantly wider than that corresponding to the n=4 case.Comment: 21 pages, 14 figure

Static Scaling Behavior of High-Molecular-Weight Polymers in Dilute Solution: A Reexamination

Previous theories of dilute polymer solutions have failed to distinguish clearly between two very different ways of taking the long-chain limit: (I) $N \to\infty$ at fixed temperature $T$, and (II) $N \to\infty$, $T \to T_\theta$ with $x \equiv N^\phi (T-T_\theta)$ fixed. I argue that the modern two-parameter theory (continuum Edwards model) applies to case II --- not case I --- and in fact gives exactly the crossover scaling functions for $x \ge 0$ modulo two nonuniversal scale factors. A Wilson-type renormalization group clarifies the connection between crossover scaling functions and continuum field theories. [Also contains a general discussion of the connection between the Wilson and field-theoretic renormalization groups. Comments solicited.]Comment: 10 pages including 1 figure, 181159 bytes Postscript (NYU-TH-93/05/01

Interacting Crumpled Manifolds: Exact Results to all Orders of Perturbation Theory

In this letter, we report progress on the field theory of polymerized tethered membranes. For the toy-model of a manifold repelled by a single point, we are able to sum the perturbation expansion in the strength g of the interaction exactly in the limit of internal dimension D -> 2. This exact solution is the starting point for an expansion in 2-D, which aims at connecting to the well studied case of polymers (D=1). We here give results to order (2-D)^4, where again all orders in g are resummed. This is a first step towards a more complete solution of the self-avoiding manifold problem, which might also prove valuable for polymers.Comment: 8 page

Evidence for ideal insulating/conducting state in a 1D integrable system

Using numerical diagonalization techniques we analyze the finite temperature/frequency conductance of a one dimensional model of interacting spinless fermions. Depending on the interaction, the observed finite temperature charge stiffness and low frequency conductance indicate a fundamental difference between integrable and non-integrable cases. The integrable systems behave as ideal conductors in the metallic regime and as ideal insulators in the insulating one. The non-integrable systems are, as expected, generic conductors in the metallic regime and activated ones in the insulating regime.Comment: revtex file, followed by 5 uuencoded postscript figure