Collapse transitions of a periodic hydrophilic hydrophobic chain

We study a single self avoiding hydrophilic hydrophobic polymer chain, through Monte-Carlo lattice simulations. The affinity of monomer i for water is characterized by a (scalar) charge , and the monomer-water interaction is short-ranged. Assuming incompressibility yields an effective short ranged interaction between monomer pairs (i,j), proportional to . In this article, we take (resp. ()) for hydrophilic (resp. hydrophobic) monomers and consider a chain with (i) an equal number of hydro-philic and -phobic monomers (ii) a periodic distribution of the along the chain, with periodicity 2p. The simulations are done for various chain lengths N, in d=2 (square lattice) and d=3 (cubic lattice). There is a critical value p _c (d,N) of the periodicity, which distinguishes between different low temperature structures. For p >p _c , the ground state corresponds to a macroscopic phase separation between a dense hydrophobic core and hydrophilic loops. For p <p _c (but not too small), one gets a microscopic (finite scale) phase separation, and the ground state corresponds to a chain or network of hydrophobic droplets, coated by hydrophilic monomers. We restrict our study to two extreme cases, and to illustrate the physics of the various phase transitions. A tentative variational approach is also presented. Received: 10 March 1998 / Received in final form: 25 June 1998 / Accepted: 1st July 1998     

Competition of disorder and interchain hopping in a two-chain Hubbard model

We study the interplay of Anderson localization and interaction in a two chain Hubbard ladder allowing for arbitrary ratio of disorder strength to interchain coupling. We obtain three different types of spin gapped localized phases depending on the strength of disorder: a pinned 4k _F Charge Density Wave (CDW) for weak disorder, a pinned 2k _F CDW^π for intermediate disorder and two independently pinned single chain 2k _F CDW for strong disorder. Confinement of electrons can be obtained as a result of strong disorder or strong attraction. We give the full phase diagram as a function of disorder, interaction strength and interchain hopping. We also study the influence of interchain hopping on localization length and show that localization is enhanced by a small interchain hopping but suppressed by a large interchain hopping. Received 6 April 2001     

Variational theory for a single polyelectrolyte chain

Variational methods are applied to a single polyelectrolyte chain. The polymer is modeled as a Gaussian chain with screened electrostatic repulsion between all monomers. As a variational Hamiltonian, the most general Gaussian kernel, including the possibility of a classical or mean polymer path, is employed. The resulting self-consistent equations are systematically solved both for large and small monomer-monomer separations along the chain. In the absence of screening, the polymer is stretched on average. It is described by a straight classical path with Gaussian fluctuations around it. If the electrostatic repulsion is screened, the polymer is isotropically swollen for large separations, and for small separations the polymer correlation function is calculated as an analytic expansion in terms of the monomer-monomer separation along the chain. The electrostatic persistence length and the electrostatic blobsize are inferred from the crossover between distinct scaling ranges. We perform a global analysis of the scaling behavior as a function of the screening length and electrostatic interaction strength , where is the Bjerrum length and A is the distance of charges along the polymer chain. We find three different scaling regimes. i) A Gaussian-persistent regime with Gaussian behavior at small, persistent behavior at intermediate, and isotropically swollen behavior at large length scales. This regime occurs for weakly charged polymers and only for intermediate values of the screening length. The electrostatic persistence length is defined as the crossover length between the persistent and the asymptotically swollen behavior and is given by and thus disagrees with previous (restricted) variational treatments which predict a linear dependence on the screening length .ii) A Gaussian regime with Gaussian behavior at small and isotropically swollen behavior at large length scales. This regime occurs for weakly charged polymers and/or strong screening, and the electrostatic repulsion between monomers only leads to subfluent corrections to Gaussian scaling at small separations. The concept of a persistence length is without meaning in this regime. iii) A persistent regime , where the chain resembles a stretched rod on intermediate and small scales. Here the persistence length is given by the original Odijk prediction, , if the overstretching of the chain is avoided. We also investigate the effects of a finite polymer length and of an additional excluded-volume interaction, which modify the resultant scaling behavior. Applications to experiments and computer simulations are discussed. Received 24 December 1997     

Adsorption of a Gaussian random copolymer chain at an interface

We consider the adsorption of an isolated, Gaussian, random, and quenched copolymer chain at an interface. We first propose a simple analytical method to obtain the adsorption/depletion transition, by averaging over the disorder the partition function instead of the free energy. The adsorption thresholds obtained by previous authors at a solid/liquid and at a liquid/liquid interface for multicopolymer chains can be rederived using this method. We also compare the adsorption thresholds obtained for bimodal and for Gaussian disorder; they only agree for small disorder. We focus on the specific case of an ideally flat asymmetric liquid/liquid interface, and consider the situation where the chain is composed of monomers of two different chemical species A and B. The replica method is developed for this case. We show that the Hartree approximation, coupled to a replica symmetry assumption, leads to the same adsorption thresholds as obtained from our general method. In order to describe the properties of the adsorbed (or depleted) chain, we develop a new approximation for long chains, within the framework of the replica theory. In most cases, the behavior of a random copolymer chain can be mapped onto that of a homopolymer chain at an asymmetric attractive interface. The values of the effective adsorption energy are different for a random and a periodic copolymer chain. Finally, we consider the case of uncorrelated annealed disorder. The behavior of an annealed chain can be mapped onto that of a homopolymer chain at an asymmetric non attractive interface; hence, an annealed chain cannot adsorb at an asymmetric interface. Received 21 January 1999     

Log-periodic oscillations for biased diffusion of a polymer chain in a porous medium

A coarse-grained off-lattice bead-spring model is used to reveal the complex dynamics of a polymer chain in a quenched porous medium in the presence of an external field B. The behavior of the mean square displacement (MSD) of the center chain bead and that of the center of mass of the chain as a function of time is studied at different values of the barrier concentration C, the field strength B and the chain length N. In a field, important information on the way in which chains move between obstacles and overcome them is gained from the MSD vs. time analysis in the directions parallel and perpendicular to the flow. Instead of a steady approach to uniform drift-like motion at low C, for sufficiently strong field B we observe logarithmic oscillations in the effective exponents describing the time dependence of the MSD along and perpendicular to field. A common nature of this phenomenon with oscillatory behavior, observed earlier for biased diffusion of tracers on random lattices, is suggested. Received 7 August 1998     

Two interacting particles in a disordered chain II: Critical statistics and maximum mixing of the one body states

For two particles in a disordered chain of length L with on-site interaction U, a duality transformation maps the behavior at weak interaction onto the behavior at strong interaction. Around the fixed point of this transformation, the interaction yields a maximum mixing of the one body states. When (the one particle localization length), this mixing results in weak chaos accompanied by multifractal wave functions and critical spectral statistics, as in the one particle problem at the mobility edge or in certain pseudo-integrable billiards. In one dimension, a local interaction can only yield this weak chaos but can never drive the two particle system to full chaos with Wigner-Dyson statistics. Received: 22 May 1998 / Received in final form: 24 August 1998 / Accepted: 4 September 1998     

Dielectric resonances in three-dimensional binary disordered media

Powdered solids often present very specific properties due to their granular nature. Such powders are often obtained by mixing two ingredients in variable proportions: conductor and insulator, or conductor and super-conductor. In a very natural way, these systems are modeled by regular lattices, whose sites or bonds are randomly chosen with given probabilities. It is known that the electrical and optical properties of random bi-dimensional (2D) networks are well described by their conductance's poles (resonances) and residues (amplitudes). The numerical implementation of a spectral method gave the spectral density, the AC conductivity, the multi-fractal properties of the moments for the local electric field (or currents), and spectrum of resonances characteristic of some small clusters (animals). This work extends the spectral method to the three-dimensional (3D) case where the problem is more complicated because the duality property and the corresponding symmetries are broken. As in the 2D-case, the two significant parameters are the ratio of the complex conductances and of both phases, and the probability p (resp. 1-p) of (resp. ). All the resonances lie on the negative real h-axis, i.e. for pure non resistive networks in the AC case. For a static (DC) system, only the value h=0 (corresponding to a binary system with finite and , or and finite) can give a resonance. Some applications are proposed, in particular the ability for small clusters (animals with one, two or three bonds) to present a singular response for well identified frequencies of the incident electromagnetic field. Received 24 March 1999     

Finite-size-scaling analyses of the chiral ordert in the Josephson-junction ladder with half a flux quantum per plaquette

Chiral order of the Josephson-junction ladder with half a flux quantum per plaquette is studied by means of the exact diagonalization method. We consider an extreme quantum limit where each superconductor grain (order parameter) is represented by S=1/2 spin. So far, the semi-classical case, where each spin reduces to a plane rotator, has been considered extensively. We found that in the case of S=1/2, owing to the strong quantum fluctuations, the chiral (vortex lattice) order becomes dissolved except in a region, where attractive intrachain and, to our surprise, repulsive interchain interactions both exist. On the contrary, for considerably wide range of parameters, the superconductor (XY) order is kept critical. The present results are regarded as a demonstration of the critical phase accompanying chiral-symmetry breaking predicted for frustrated XXZ chain field-theoretically. Received 20 February 2000     

Polymer adsorption on heterogeneous surfaces

The adsorption of a single ideal polymer chain on energetically heterogeneous and rough surfaces is investigated using a variational procedure introduced by Garel and Orland (Phys. Rev. B 55, 226 (1997)). The mean polymer size is calculated perpendicular and parallel to the surface and is compared to the Gaussian conformation and to the results for polymers at flat and energetically homogeneous surfaces. The disorder-induced enhancement of adsorption is confirmed and is shown to be much more significant for a heterogeneous interaction strength than for spatial roughness. This difference also applies to the localization transition, where the polymer size becomes independent of the chain length. The localization criterion can be quantified, depending on an effective interaction strength and the length of the polymer chain. Received: 29 October 1997 / Revised: 19 December 1997 / Accepted: 6 March 1998     

Field-induced winding of chiral polymers

We propose a microscopic model of a chiral polymer chain with permanent transverse dipoles interacting with an external electric field. Its behaviour has been investigated by computer simulation in the limit of weak chirality. Large-scale (tertiary) helical winding induced along the field direction has been found above a threshold field E_c, and the helix parameters have been calculated as functions of the field strength. Below E_c there is no coherent helical structure of the chain conformation. We find a characteristic scaling of the threshold and the winding radius a with the chain bending modulus , and . Received: 15 November 1997 / Accepted: 16 February 1998     

Multiple conformations in polyampholytes

We study the configurational statistics of a ring polyampholyte chain made of N randomly charged monomers with elementary charge .To a large extent, the overall structure of a polyampholyte is controlled by a total sum Q of all charges. When the total charge is smaller than , the polyampholyte has a compact globular structure. At charges larger than , the configuration has the form of a ring of small globules (beads) connected by strings. Between Q₁ and Q₂ we find a remarkable diversity of meta-stable configurations having the shapes of irregular clusters of small globules connected by the strings. We estimate the number of these configurations and the energy barriers between them. Between Q₁ and Q₂, the minimum energy configurations are completely controlled by randomness in the charge distribution along the chain. There are hysteresis effects in the shapes of the clusters. As the total charge increases, the linearly extended configurations become dynamically more preferable. When the charge decreases, the circular shapes are preferred. We remark on the probable connection with the multiple phase transitions observed in polyampholyte gels. Received: 10 July 1997 / Accepted: 13 October 1997     

Coulomb repulsion versus Hubbard repulsion in a disordered chain

We study the difference between on site Hubbard and long range Coulomb repulsions for two interacting particles in a disordered chain. The system size L (in units of the lattice spacing) is of the order of the one particle localization length and the energies are taken near the band center. In the two cases, the limits of weak and strong interactions are characterized by uncorrelated energy levels and are separated by a crossover regime where the states are more extended and the spectra more rigid. U denoting the interaction strength and t the kinetic energy scale, the crossovers take place for interaction energy to kinetic energy ratios U/t and U/(2tL) of order one, for Hubbard and Coulomb repulsions respectively. While Hubbard repulsion can only yield weak critical chaos with intermediate spectral statistics, Coulomb repulsion can drive the two particle system to quantum chaos with Wigner-Dyson spectral statistics. The interaction matrix elements are studied to explain this difference. Received 21 March 2000 and Received in final form 5 February 2001     

Molecular-dynamics simulation of a glassy polymer melt: Incoherent scattering function

We present simulation results for a model polymer melt, consisting of short, nonentangled chains, in the supercooled state. The analysis focuses on the monomer dynamics, which is monitored by the incoherent intermediate scattering function. The scattering function is recorded over six decades in time and for many different wave-vectors which range from the size of a chain to about three times the maximum position of the static structure factor. The lowest temperatures studied are slightly above , the critical temperature of mode-coupling theory (MCT), where was determined from a quantitative analysis of the - and -relaxations. We find evidence for the space-time factorization theorem in the -relaxation regime, and for the time-temperature superposition principle in the -regime, if the temperature is not too close to . The wave-vector (q-) dependence of the nonergodicity parameter, of the critical amplitude, and the -relaxation time are in qualitative agreement with calculations for hard spheres. For q larger than the maximum of the structure factor the -relaxation time already agrees fairly well with the asymptotic MCT-prediction . The behavior of the relaxation time at small q can be rationalized by the validity of the Gaussian approximation and the value of the Kohlrausch stretching exponent, as suggested in neutron-scattering experiments. Received 30 October 1998     

Anomalous viscosity exponent in a discretized model for a chain diffusion in one dimension

We present a one-dimensional Monte Carlo simulation for the diffusion motion of a chain of N beads. We found that the scaling exponent for the viscosity can be smaller or greater than 3. This anomalous behavior cannot be attributed to the diffusivity scaling or the length fluctuations but is due to the chain dynamics details during diffusion in which the end beads play the key role. The viscosity exponent 3 and its expected relation with the diffusivity exponent are recovered in the asymptotic regime (N ↦∞). Received 24 September 2001 and Received in final form 28 January 2002     

Water droplets in a spherically confined nematic solvent: A numerical investigation

Recently, it was observed that water droplets suspended in a nematic liquid crystal form linear chains [Poulin et al., Science 275, 1770 (1997)]. The chaining occurs, e.g., in a large nematic drop with homeotropic boundary conditions at all the surfaces. Between each pair of water droplets a point defect in the liquid crystalline order was found in accordance with topological constraints. This point defect causes a repulsion between the water droplets. In our numerical investigation we limit ourselves to a chain of two droplets. For such a complex geometry we use the method of finite elements to minimize the Frank free energy. We confirm an experimental observation that the distance d of the point defect from the surface of a water droplet scales with the radius r of the droplet like .When the water droplets are moved apart, we find that the point defect does not stay in the middle between the droplets, but rather forms a dipole with one of them. This confirms a theoretical model for the chaining. Analogies to a second order phase transition are drawn. We also find the dipole when one water droplet is suspended in a bipolar nematic drop with two boojums, i.e., surface defects at the outer boundary. Finally, we present a configuration where two droplets repel each other without a defect between them. Received 11 December 1998     

Interaction induced delocalization of two particles: large system size calculations and dependence on interaction strength

The localization length L₂ of two interacting particles in a one-dimensional disordered system is studied for very large system sizes by an efficient and accurate variant of the Green function method. The numerical results (at the band center) can be well described by the functional form L ₂ =L ₁ [0.5+c(U) L ₁ ] where L₁ is the one-particle localization length and the coefficient depends on the strength U of the on-site Hubbard interaction. The Breit-Wigner width or equivalently the (inverse) life time of non-interacting pair states is analytically calculated for small disorder and taking into account the energy dependence of the one-particle localization length. This provides a consistent theoretical explanation of the numerically found U-dependence of c(U). Received 16 September 1998     

A new simulation method for the determination of forces in polymer/colloid systems

We introduce a new simulation method, which we call the contact-distribution method, for the determination of the Helmholtz potential for polymer/colloid systems from lattice Monte-Carlo simulations. This method allows one to obtain forces between finite or semi-infinite objects of any arbitrary shape and dimensions in the presence of polymer chains in solution or physisorbed or chemisorbed at interfaces. We illustrate the application of the method using two examples: (i) the interaction between the tip of an atomic force microscope (AFM) and a single, end-grafted polymer chain and (ii) the interaction between an AFM tip and a polymer brush. Numerical results for the first two cases illustrate how the method can be used to confirm and extend scaling laws for forces and Helmholtz potentials, to examine the effects of the shapes and sizes of the objects and to examine conformational transitions in the polymer chains. Received: 15 May 1998 / Revised: 11 June 1998 / Accepted: 12 June 1998     

Fermi liquid theory: a renormalization group approach

We show how Fermi liquid theory results can be systematically recovered using a renormalization group (RG) approach. Considering a two-dimensional system with a circular Fermi surface, we derive RG equations at one-loop order for the two-particle vertex function in the limit of small momentum () and energy () transfer and obtain the equation which determines the collective modes of a Fermi liquid. The density-density response function is also calculated. The Landau function (or, equivalently, the Landau parameters F _l ^s and F _l ^a ) is determined by the fixed point value of the -limit of the two-particle vertex function (). We show how the results obtained at one-loop order can be extended to all orders in a loop expansion. Calculating the quasi-particle life-time and renormalization factor at two-loop order, we reproduce the results obtained from two-dimensional bosonization or Ward Identities. We discuss the zero-temperature limit of the RG equations and the difference between the Field Theory and the Kadanoff-Wilson formulations of the RG. We point out the importance of n-body () interactions in the latter. Received: 27 June 1997 / Received in final form: 17 December 1997 / Accepted: 26 January 1998