Polyelectrolyte chains in poor solvent. A variational description of necklace formation

We study the properties of polyelectrolyte chains under different solvent conditions, using a variational technique. The free energy and the conformational properties of a polyelectrolyte chain are studied by minimizing the free energy F_N, depending on N(N - 1)/2 trial probabilities that characterize the conformation of the chain. The Gaussian approximation is considered for a ring of length 2⁴ < N < 2⁸ and for an open chain of length 50 < N < 200 in poor- and theta-solvent conditions, including a Coulomb repulsion between the monomers. In theta-solvent conditions the blob size is measured and found in agreement with scaling theory, including charge depletion effects, expected for the case of an open chain. In poor-solvent conditions, a globule instability, driven by electrostatic repulsion, is observed. We notice also inhomogeneous behavior of the monomer-monomer correlation function, reminiscence of necklace formation in poor-solvent polyelectrolyte solutions. A global phase diagram in terms of solvent quality and inverse Bjerrum length is presented. Received 7 June 2001 and Received in final form 17 October 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     

Universality in diffusion front growth dynamics

We have studied the scaling properties of diffusion fronts by numerical calculations based on the mean field approach in the context of a lattice gas model, performed in a triangular lattice. We find that the height-height correlation function scales with time t and length l as C(l, t) ≈l ^α f (t/l ^α/β) with α = 0.62±0.01 and β = 0.39±0.02. These exponent values are identical to those characterising the roughness of the diffusion fronts evolving through a square lattice [1,2], thus confirming their universality. Received 14 November 2001 / Received in final form 20 April 2002 Published online 31 July 2002     

Adsorption of a semiflexible wormlike chain

Adsorption of ideal polymers with stiff backbone onto a flat surface is considered theoretically. Both scaling approach and quantitative theory are developed. We predict a self-similar monomer concentration profile c(x) ∼ x ^-4/3 near the surface (when the distance to the surface x is much smaller than the chain persistence length l /2). The typical conformation of a weakly adsorbed chain can be viewed as a sequence of alternating flat (2-dimensional) trains of wormlike short loops (flat blobs) and coil-like (3-dimensional) loops forming a triple-layer structure: contact layer (x < Δ) of adsorbed fragments virtually laid on the surface, proximal layer (Δ < x < l) of flat blobs, and more dilute distal corona layer (x > l). Here Δ defines the range of monomer/surface attraction, Δ ≪ l. The adsorption transition is continuous. However, its relative width is small (T ^* is the adsorption temperature, ΔT is the relevant temperature interval): ∼ , i.e. a discontinuous transition in the limit Δ/l↦ 0. Received 10 October 2002 and Received in final form 22 November 2002 RID="a" ID="a"Permanent address: Physics Department, Moscow State University, Moscow 119992, Russia. e-mail: semenov@polly.phys.msu.ru     

Radial distribution function of rod-like polyelectrolytes

We study the effect of electrostatic interactions on the distribution function of the end-to-end distance of a single polyelectrolyte chain in the rod-like limit. The extent to which the radial distribution function of a polyelectrolyte is reproduced by that of a wormlike chain with an adjusted effective persistence length is investigated. Strong evidence is found for a universal scaling formula connecting the effective persistence length of a polyelectrolyte with the strength of the electrostatic interaction and the Debye screening length. Received 4 March 2002 and Received in final form 1 July 2002 RID="a" ID="a"e-mail: jrudnick@physics.ucla.edu     

Positron spectra from internal pair conversion observed in 238U + 181Ta collisions

We present new results from measurements and simulations of positron spectra, originating from ²³⁸U + ¹⁸¹Ta collisions at beam energies close to the Coulomb barrier. The measurements were performed using an improved experimental setup at the double-Orange spectrometer of GSI. Particular emphasis is put on the signature of positrons from Internal-Pair-Conversion (IPC) processes in the measured e⁺-energy spectra, following the de-excitation of electromagnetic transitions in the moving Ta-like nucleus. It is shown by Monte Carlo simulations that, for the chosen current sweeping procedure used in the present experiments, positron emission from discrete IPC transitions can lead to rather narrow line structures in the measured energy spectra. The measured positron spectra do not show evidence for line structures within the statistical accuracy achieved, although expected from the intensities of the observed γ-transitions ( E _γ∼ 1250-1600 keV) and theoretical conversion coefficients. This is due to the reduced detection efficiency for IPC positrons, caused by the limited spatial and momentum acceptance of the spectrometer. A comparison with previous results, in which lines have been observed, is presented and the implications are discussed. Received: 27 April 2000 / Accepted: 14 September 2000     

Weak violation of universality for polyelectrolyte chains: Variational theory and simulations

A variational approach is considered to calculate the free energy and the conformational properties of a polyelectrolyte chain in d dimensions. We consider in detail the case of pure Coulombic interactions between the monomers, when screening is not present, in order to compute the end-to-end distance and the asymptotic properties of the chain as a function of the polymer chain length N. We find R≃N ^ν(log N)^γ, where ν = and λ is the exponent which characterizes the long-range interaction U∝ 1/r ^λ. The exponent γ is shown to be non-universal, depending on the strength of the Coulomb interaction. We check our findings by a direct numerical minimization of the variational energy for chains of increasing size 2⁴ < N < 2¹⁵. The electrostatic blob picture, expected for small enough values of the interaction strength, is quantitatively described by the variational approach. We perform a Monte Carlo simulation for chains of length 2⁴ < N < 2¹⁰. The non-universal behavior of the exponent γ previously derived within the variational method is also confirmed by the simulation results. Non-universal behavior is found for a polyelectrolyte chain in d = 3 dimension. Particular attention is devoted to the homopolymer chain problem, when short-range contact interactions are present. Received 8 August 2000 and Received in final form 19 December 2000     

On the theory of light scattering in molecular liquids

The theory of light scattering for a system of linear molecules with anisotropic polarizabilities is considered. As a starting point for our theory, we express the result of a scattering experiment in VV and VH symmetry as dynamic correlation functions of tensorial densities ρ _lm(q) with l = 0 and l = 2. l, m denote indices of spherical harmonics. To account for all observed hydrodynamic singularities, a generalization of the theory of Schilling and Scheidsteger [1] for these correlation functions is presented, which is capable to describe the light scattering experiments from the liquid regime to the glassy state. As a microscopic theory it fulfills all sum rules contrary to previous phenomenological theories. We emphasize the importance of the helicity index m for the microscopic theory by showing, that only the existence of m = 1 components lead to the well known Rytov dip in liquids and to the appearance of transversal sound waves in VH symmetry in the deeply supercooled liquid and the glass. Exact expressions for the phenomenological frequency dependent rotation translation coupling coefficients of previous theories are derived. Received 3 July 2000 and Received in final form 7 November 2000     

Energy landscapes, lowest gaps, and susceptibility of elastic manifolds at zero temperature

We study the effect of an external field on (1 + 1) and (2 + 1) dimensional elastic manifolds, at zero temperature and with random bond disorder. Due to the glassy energy landscape the configuration of a manifold changes often in abrupt, “first order”-type of large jumps when the field is applied. First the scaling behavior of the energy gap between the global energy minimum and the next lowest minimum of the manifold is considered, by employing exact ground state calculations and an extreme statistics argument. The scaling has a logarithmic prefactor originating from the number of the minima in the landscape, and reads ΔE ₁∼L ^θ[ln(L _z L ^{- ζ})]^-1/2, where ζ is the roughness exponent and θ is the energy fluctuation exponent of the manifold, L is the linear size of the manifold, and L_z is the system height. The gap scaling is extended to the case of a finite external field and yields for the susceptibility of the manifolds ∼L ^{2D + 1 - θ}[(1 - ζ)ln(L)]^1/2. We also present a mean field argument for the finite size scaling of the first jump field, h ₁∼L ^{d - θ}. The implications to wetting in random systems, to finite-temperature behavior and the relation to Kardar-Parisi-Zhang non-equilibrium surface growth are discussed. Received December 2000 and Received in final form April 2001     

A relativistic quark model for mesons with an instanton-induced interaction

We present new results of a relativistic quark model based on the Bethe-Salpeter equation in its instantaneous approximation. Assuming a linearly rising confinement potential with an appropriate spinorial structure in Dirac space and adopting a residual interaction based on instanton effects, we can compute masses of the light mesons up to highest observed angular momenta with a natural solution of the U _A(1) problem. The calculated ground states masses and the radial excitations describe the experimental results well. In this paper, we will also discuss our results concerning numerous meson decay properties. For processes like π⁺/K ⁺↦e ⁺υ_eγ and 0^-↦γγ at various photon virtualities, we find a good agreement with experimental data. We will also comment on the form factors of the K _?3 decay and on the decay constants of the π, K and η mesons. For the sake of completeness, we will furthermore present the electromagnetic form factors of the charged π and K mesons as well as a comparison of the radiative meson decay widths with the most recent experimental data. Received: 28 August 2000 / Accepted: 12 September 2000     

Flexible linear polyelectrolytes in multivalent salt solutions: Solubility conditions

Single- and double-stranded DNA and many biological and synthetic polyelectrolytes undergo two structural transitions upon increasing the concentration of multivalent salt or molecules. First, the expanded-stretched chains in low monovalent salt solutions collapse into nearly neutral compact structures when the density of multivalent salt approaches that of the monomers. With further addition of multivalent salt the chains redissolve acquiring expanded-coiled conformations. We study the redissolution transition using a two-state model (F.J. Solis, M. Olvera de la Cruz, J. Chem. Phys. 112, 2030 (2000)). The redissolution occurs when there is a high degree of screening of the electrostatic interactions between monomers, thus reducing the energy of the expanded state. The transition is determined by the chemical potential of the multivalent ions in the solution, μ and the inverse screening length, κ. The transition point also depends on the charge distribution along the chain but is nearly independent of the molecular weight and degree of flexibility of the polyelectrolytes. We generate a diagram of μversusκ² where we find two regions of expanded conformations, one with charged chains and the other with overcharged (inverted charge) chains, separated by a collapsed nearly neutral conformation region. The collapse and redissolution transitions occur when the trajectory of the properties of the salt crosses the boundaries between these regions. We find that in most cases the redissolution occurs within the same expanded branch from which the chain precipitates. Received 15 May 2000 and Received in final form 28 June 2000     

Finite-size scaling of the level compressibility at the Anderson transition

We compute the number level variance Σ ₂ and the level compressibility χ from high precision data for the Anderson model of localization and show that they can be used in order to estimate the critical properties at the metal-insulator transition by means of finite-size scaling. With N, W, and L denoting, respectively, linear system size, disorder strength, and the average number of levels in units of the mean level spacing, we find that both χ(N, W) and the integrated Σ ₂ obey finite-size scaling. The high precision data was obtained for an anisotropic three-dimensional Anderson model with disorder given by a box distribution of width W/2. We compute the critical exponent as ν≈ 1.45±0.12 and the critical disorder as W _c≈ 8.59±0.05 in agreement with previous transfer-matrix studies in the anisotropic model. Furthermore, we find χ≈ 0.28±0.06 at the metal-insulator transition in very close agreement with previous results. Received 1st November 2001 and Received in final form 8 March 2002 Published online 6 June 2002     

From independent particle towards collective motion for two polarized electrons on a square lattice

The two dimensional crossover from independent particle towards collective motion is studied using 2 polarized electrons (spinless fermions) interacting via a U/r Coulomb repulsion in a L×L square lattice with periodic boundary conditions and nearest neighbor hopping t. Three regimes characterize the ground state when U/t increases. Firstly, when the fluctuation Δr of the spacing r between the two particles is larger than the lattice spacing a, there is a scaling length L ₀ = π²(t/U) such that the relative fluctuation Δr/〈r〉 is a universal function of the dimensionless ratio L/L ₀, up to finite size corrections of order L^-2. L < L ₀ and L > L ₀ are respectively the limits of the free particle Fermi motion and of the correlated motion of a Wigner molecule. Secondly, when U/t exceeds a threshold U ^*(L)/t, Δr becomes smaller than a, giving rise to a correlated lattice regime where the previous scaling breaks down and analytical expansions in powers of t/U become valid. A weak random potential reduces the scaling length and favors the correlated motion. Received 28 March 2002 Published online 19 November 2002     

First energy and angle differential measurements of e+e−-pairs emitted by internal pair conversion of excited heavy nuclei

We present the first energy and angle resolved measurements of e⁺e⁻-pairs emitted from heavy nuclei (Z≥ 40) at rest by internal pair conversion (IPC) of transitions with energies of less than 2 MeV as well as recent theoretical results using the DWBA method, which takes full account of relativistic effects, magnetic substates and finite size of the nucleus. The 1.76 MeV E0 transition in ⁹⁰Zr (⁹⁰Sr source) and the 1.77 MeV M1 transition in ²⁰⁷Pb (²⁰⁷Bi source) have been investigated experimentally using the essentially improved setup at the double-ORANGE β-spectrometer of GSI. The measurements prove the capability of the setup to cleanly identify the IPC pairs in the presence of five orders of magnitude higher β⁻ and γ background from the same source and to yield essentially background-free sum spectra despite the large background. Using the ability of the ORANGE setup to directly determine the opening angle of the e⁺e⁻–pairs (Θ_e+e−), the angular correlation of the emitted pairs was measured within the range covered experimentally (40°≤Θ_e+e−≤ 180°). In the ⁹⁰Zr case the correlation could be deduced for a wide range of energy differences E _Δ of the pairs (−530 keV ≤E _Δ≤ 530 keV). The ⁹⁰Zr results are in good agreement with recent theory. The angular correlation deduced for the M1 transition in ²⁰⁷Pb is in strong disagreement with theoretical predictions derived within the Born approximation and shows almost isotropic character. This is again in agreement with the new theoretical results. Received: 22 April 1997 / Revised version: 16 December 1997     

Weak e+e− lines from internal pair conversion observed in collisions of 238U with heavy nuclei

We present the results of a Doppler-shift correction to the measured e⁺e⁻–sum-energy spectra obtained from e⁺e⁻–coincidence measurements in ²³⁸U +²⁰⁶Pb and ²³⁸U +¹⁸¹Ta collisions at beam energies close to the Coulomb barrier, using an improved experimental setup at the double-Orange spectrometer of GSI. Internal-Pair-Conversion (IPC) e⁺e⁻ pairs from discrete nuclear transitions of a moving emitter have been observed following Coulomb excitation of the 1.844 MeV (E1) transition in ²⁰⁶Pb and neutron transfer to the 1.770 MeV (M1) transition in ²⁰⁷Pb. In the collision system ²³⁸U +¹⁸¹Ta, IPC transitions were observed from the Ta-like as well as from the U-like nuclei. In all systems the Doppler-shift corrected e⁺e⁻–sum-energy spectra show weak lines at the energies expected from the corresponding γ–ray spectra with cross sections being consistent with the measured excitation cross sections of the γ lines and the theoretically predicted IPC coefficients. No other than IPC e⁺e⁻–sum-energy lines were found in the measured spectra. The transfer cross sections show a strong dependence on the distance of closest approach (R_min), thus signaling also a strong dependence on the bombarding energy close to the Coulomb barrier. Received: 22 July 1997 / Revised version: 15 October 1997     

Relation between vortex excitation and thermal conductivity in superconductors

Thermal conductivity κ _xx(T) under a field is investigated in d _{x2 - y2}-wave superconductors and isotropic s-wave superconductors by the linear response theory, using a microscopic wave function of the vortex lattice states. To study the origin of the different field dependence of κ_xx(T) between higher and lower temperature regions, we analyze the spatially-resolved thermal conductivity around a vortex at each temperature, which is related to the spectrum of the local density of states. We also discuss the electric conductivity in the same formulation for a comparison. Received 8 December 2001 and Received in final form 20 March 2002 Published online 6 June 2002     

Determination of the neutron electric form factor from the reaction 3 He(e,e'n) at medium momentum transfer

The electric form factor of the neutron G_En has been determined in double polarized exclusive ³ He(e,e'n) scattering in quasi–elastic kinematics by measuring asymmetries A _⊥, A _∥ of the cross section with respect to helicity reversal of the electron, with the nuclear spin being oriented perpendicular to the momentum transfer q in case of A_⊥ and parallel in case of A_∥. The experiment was performed at the 855 MeV c. w. microtron MAMI at Mainz. The degree of polarization of the electron beam and of the gaseous ³ He target were each about 50%. Scattered electrons and neutrons were detected in coincidence by detector arrays covering large solid angles. Quasi–elastic scattering events were reconstructed from the measured electron scattering angles ϑ_e, φ_e and the neutron momentum vector p _n ^′ in the plane wave impulse approximation. We obtain the result <G _En>_{(0.27 < Q2c2/GeV2 < 0.5)}= 0.0334 ± 0.0033_stat± 0.0028_syst which is averaged over the indicated range of Q ², the squared momentum transfer. This G _En value is significantly smaller than measured from the D(e,e'n) reaction under similar kinematical conditions. To what extent final state interactions in ³He quench the G _En result is subject of calculations currently in progress elsewhere. Received: 29 April 1999     

Effective nonlinear optical properties of shape distributed composite media

The effective linear and nonlinear optical properties of metal/dielectric composite media, in which ellipsoidal metal inclusions are distributed in shape, are investigated. The shape distribution function P(L _x, L _y) is assumed to be 2Δ^-2θ(L _x - 1/3 + Δ/3)θ(L _y - 1/3 + Δ/3)θ(2/3 + Δ/3 - L _x - L _y), where θ( ^{. . .} ) is the Heaviside function, Δ is the shape variance and L_i are the depolarization factors of the ellipsoidal inclusions along i-symmetric axes (i = x, y). Within the spectral representation, we adopt Maxwell-Garnett type approximation to study the effect of shape variance Δ on the effective nonlinear optical properties. Numerical results show that both the effective linear optical absorption α ∼ ωIm() and the modulus of the effective third-order optical nonlinearity enhancement |χ⁽³⁾ _e|/χ⁽³⁾ ₁ exhibit the nonmonotonic behavior with Δ. Moreover, with increasing Δ, the optical absorption and the nonlinearity enhancement bands become broad, accompanied with the decrease of their peaks. The adjustment of Δ from 0 to 1 allows us to examine the crossover behavior from no separation to large separation between optical absorption and nonlinearity enhancement peaks. As Δ → 0, i.e., the ellipsoidal shape deviates slightly from the spherical one, the dependence of |χ⁽³⁾ _e|/χ⁽³⁾ ₁ on Δ becomes strong first and then weak with increasing the imaginary part of inclusions' dielectric constant. In the dilute limit, the exact formula for the effective optical nonlinearity is derived, and the present approximation characterizes the exact results better than old mean field one does. Received 10 December 2002 Published online 4 June 2003 RID="a" ID="a"e-mail: lgaophys@pub.sz.jsinfo.net     

High frequency sound and the boson peak in amorphous silica

We present the results of extensive molecular dynamics computer simulations in which the high frequency dynamics of silica, i.e. for frequencies ν > 0.5 THz, is investigated in the viscous liquid state as well as in the glass state. We characterize the properties of high frequency sound modes by analyzing J _l(q,ν) and J _t(q,ν), the longitudinal and transverse current correlation function, respectively. For wave-vectors q > 0.4 ?^-1 the spectra are sitting on top of a flat background. The dynamic structure factor S(q,ν) exhibits for q > 0.23 ?^-1 a boson peak which is located nearly independent of q around 1.7 THz and for which the intensity scales approximately linearly with temperature. We show that the low frequency part of the boson peak is mainly due to the elastic scattering of transverse acoustic modes with frequencies around 1 THz. The strength of this scattering depends on q and is largest around q = 1.7 ?^-1, the location of the first sharp diffraction peak in the static structure factor. By studying S(q,ν) for different system sizes we show that strong finite size effects are present in the low frequency part of the boson peak in that for small systems part of its intensity is missing. We discuss the consequences of these finite size effects for the structural relaxation. Received 27 June 2000 and Received in final form 9 January 2001     

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