Reaction kinetics in polymer melts

We study the reaction kinetics of end-functionalized polymer chains dispersed in an unreactive polymer melt. Starting from an infinite hierarchy of coupled equations for many-chain correlation functions, a closed equation is derived for the 2nd order rate constant k after postulating simple physical bounds. Our results generalize previous 2-chain treatments (valid in dilute reactants limit) by Doi [#!doi:inter2!#], de Gennes [#!gennes:polreactionsiandii!#], and Friedman and O'Shaughnessy [#!ben:interdil_all_aip!#], to arbitrary initial reactive group density n₀ and local chemical reactivity Q. Simple mean field (MF) kinetics apply at short times, .For high Q, a transition occurs to diffusion-controlled (DC) kinetics with (where x_t is rms monomer displacement in time t) leading to a density decay . If n₀ exceeds the chain overlap threshold, this behavior is followed by a regime where during which k has the same power law dependence in time, , but possibly different numerical coefficient. For unentangled melts this gives while for entangled cases one or more of the successive regimes ,t ^-3/8 and t ^-3/4 may be realized depending on the magnitudes of Q and n₀. Kinetics at times longer than the longest polymer relaxation time are always MF. If a DC regime has developed before then the long time rate constant is where R is the coil radius. We propose measuring the above kinetics in a model experiment where radical end groups are generated by photolysis. Received: 2 June 1998 / Revised: 9 July 1998 / Accepted: 10 July 1998     

Light-induced bistability in spin transition solids leading to thermal and optical hysteresis

We investigate the behaviour of photo-excitable, bistable systems, under permanent light irradiation, in presence of relaxation towards the non-excited state. Cooperativity causes bistability of the steady state, leading to light-induced thermal and optical hysteresis (LITH and LIOH). The light-induced instability is expected to induce demixtion, i.e. the coexistence of domains of the two stable steady states. Such effects are evidenced by magnetic and reflectivity measurements on the spin-crossover solid solution: , with x= 0.3, 0.5, 0.85. Experimental data are in quantitative agreement with a simple macroscopic model which includes a non-linear relaxation term in the master equation. Received: 5 June 1997 / Accepted: 17 July 1998     

Shear banding instability in wormlike micellar solutions

Using NMR velocimetry and mechanical measurements we study the flow dynamics, within a cone-and-plate rheometer, of the wormlike micelle system, cetylpyridinium chloride/sodium salicylate (CPyCl/NaSal) at 100 mM/60 mM concentration in distilled water. Depending on precise conditions within the system, two classes of behaviour are observed, one in which the boundary between different shear rate phases fluctuates rapidly (on the order of tens of milliseconds) and one in which it migrates slowly with a time constant of many seconds. These modes of behaviour may depend on minor solution impurities, which presumably affect the detailed constitutive properties, but also on the externally applied shear rate within a given system. We argue that the slow migrations are governed by stress relaxation effects while the rapid migrations are flow driven and arise from interfacial instability. Received: 2 June 1998 / Received in final form and Accepted: 27 July 1998     

Using continuous control for amplification and displacement of chaotic signals

Continuous control, used on chaotic systems that bear some special symmetries, gives rise to interesting generalized synchronization behaviors which include modification of signal amplitudes, and trajectories of the system being controlled that reproduce the controller attractor in a region of phase space out of the region where it is stable. Theoretical reasoning and computer simulations show how continuous control methods can be used to obtain these generalized synchronization behaviors, and to tune the desired degree of amplification or displacement. Moreover it is shown that these behaviors can be asymptotically stable, and very robust against external noise and mismatches in the controlling arrangement. Received: 11 March 1998 / Revised: 9 July 1998 / Accepted: 13 July 1998     

Lévy-flight spreading of epidemic processes leading to percolating clusters

We consider two stochastic processes, the Gribov process and the general epidemic process, that describe the spreading of an infectious disease. In contrast to the usually assumed case of short-range infections that lead, at the critical point, to directed and isotropic percolation respectively, we consider long-range infections with a probability distribution decaying in d dimensions with the distance as . By means of Wilson's momentum shell renormalization-group recursion relations, the critical exponents characterizing the growing fractal clusters are calculated to first order in an -expansion. It is shown that the long-range critical behavior changes continuously to its short-range counterpart for a decay exponent of the infection . Received: 17 July 1998 / Revised: 20 July 1998 / Accepted: 28 July 1998     

Wavenumber dependence of structural relaxation in a molecular liquid

Structural relaxation in liquid orthoterphenyl is studied by means of coherent neutron time-of-flight and backscattering spectroscopy over a large temperature range. Not only amplitude and relaxation time but also the spectral line shape show a significant variation with wavenumber. These variations are correlated with the static structure factor, in qualitative accord with mode-coupling results for simple liquids. Even far above the melting point, relaxation remains non-exponential. Received: 5 January 1998 / Revised: 3 April 1998 / Accepted: 19 June 1998     

Dynamic response of an irreversible reaction system to a pulsed perturbation

The dynamic response of the ZGB surface reaction lattice gas model, for the catalyzed reaction , is studied by means of Monte-Carlo simulations in the neighborhood of its second order irreversible phase transition (IPT). It is found that shortly after driving a stationary configuration into the absorbing state, the relaxation of the system can be well described by a stretched exponential behavior. The dependence of the relaxation characteristic time and the induced changes on the coverage of the reactants, on both, the intensity and the period of the pulsed perturbation, are systematically investigated. The obtained insights can straightforwardly be extended to a wide variety of irreversible systems exhibiting second order IPT's, such as directed percolation, forest fire models, the contact process, branching annihilating walkers, catalyzed reactions, etc. Received 6 July 1998     

Quantum scattering in the strip: From ballistic to localized regimes

Quantum scattering is studied in a system consisting of randomly distributed point scatterers in the strip. The model is continuous yet exactly solvable. Varying the number of scatterers (the sample length) we investigate a transition between the ballistic and the localized regimes. By considering the cylinder geometry and introducing the magnetic flux we are able to study time reversal symmetry breaking in the system. Both macroscopic (conductance) and microscopic (eigenphases distribution, statistics of S-matrix elements) characteristics of the system are examined. Received: 28 January 1998 / Revised: 16 June 1998 / Accepted: 6 July 1998     

Swollen-collapsed transition in random hetero-polymers

A lattice model of a hetero-polymer with random hydrophilic-hydrophobic charges interacting with the solvent is introduced, whose continuum counterpart has been proposed by Garel, Leibler and Orland [#!GLO!#]. The transfer matrix technique is used to study various constrained annealed systems which approximate at various degrees of accuracy the original quenched model. For highly hydrophobic chains an ordinary -point transition is found from a high temperature swollen phase to a low temperature compact phase. Depending on the type of constrained averages, at very low temperatures a swollen phase or a coexistence between compact and swollen phases are found. The results are carefully compared with the corresponding ones obtained in the continuum limit, and various improvements in the original calculations are discussed. Received: 10 April 1998 / Revised: 4 June 1998 / Accepted: 1st July 1998     

Photon statistics of a bad-cavity laser near threshold

A simple model of a bad-cavity laser is presented based on Haken's master equation for N pumped two-level atoms in a cavity. Via adiabatic elimination of fast variables the whole photon statistics is solved analytically near threshold. It is shown that the second order coherence function g ⁽²⁾ (0) has a very different behavior near threshold for a bad-cavity laser compared to a good-cavity laser. The power spectrum illustrates nicely the different time scales involved in the dynamics. Received: 13 November 1998 / Revised: 19 May 1998 / Accepted: 6 July 1998     

The and transitions in the oxygen isoelectronic sequence

Multiconfiguration Dirac-Fock results are reported for the and transitions in the oxygen-like sequence for Z =9,...,18. Both transition energies and transition rates are included. Received: 29 June 1998 / Accepted: 1st July 1998     

Damage-spreading in the Bak-Sneppen model without noise

We study the behavior under perturbations in the, recently introduced, Bak-Sneppen model with deterministic updating. We focus our attention on the damage-spreading features and show that the value of the growth exponent for the distance, , coincides with that of the random updating Bak-Sneppen model. Moreover, we generalize this analysis by considering a broader set of initial perturbations for which the value of is preserved. Received: 24 June 1998 / Accepted: 9 July 1998     

Photoemission, inverse photoemission and superconducting correlations in Hubbard and t-J ladders: role of the anisotropy between legs and rungs

Several experiments in the context of ladder materials have recently shown that the study of simple models of anisotropic ladders (i.e. with different couplings along legs and rungs) is important for the understanding of these compounds. In this paper Exact Diagonalization studies of the one-band Hubbard and t-J models are reported for a variety of densities, couplings, and anisotropy ratios. The emphasis is given to the one-particle spectral function which presents a flat quasiparticle dispersion at the chemical potential in some region of parameter space. This is correlated with the existence of strong pairing fluctuations, which themselves are correlated with an enhancement of the bulk-extrapolated value for the two-hole binding energy as well as with the strength of the spin-gap in the hole-doped system. Part of the results for the spectral function are explained using a simple analytical picture valid when the hopping along the legs is small. In particular, this picture predicts an insulating state at quarter filling in agreement with the metal-insulator transition observed at this special filling for increasing rung couplings. The results are compared against previous literature, and in addition pair-pair correlations using extended operators are also here reported. Received: 22 April 1998 / Revised: 23 July 1998 / Accepted: 30 July 1998     

On charged mesoscopic metallic bubbles

We investigate the existence of stable charged metallic bubbles using the shell correction method. We find that for a given mesoscopic system of n atoms of a given metal and (positive) elementary charges, a metallic bubble turns out to have a lower total energy than a compact spherical cluster, whenever the charge number q is larger than a critical charge number q_c. For a magic number (n-q) of free electrons, the spherical metallic bubble may become stable against fission. Received: 17 November 1997 / Revised: 28 May 1998 / Accepted: 20 July 1998     

Block persistence

We define a block persistence probability p _l (t) as the probability that the order parameter integrated on a block of linear size l has never changed sign since the initial time in a phase-ordering process at finite temperature T<T _c . We argue that in the scaling limit of large blocks, where z is the growth exponent (), is the global (magnetization) persistence exponent and f(x) decays with the local (single spin) exponent for large x. This scaling is demonstrated at zero temperature for the diffusion equation and the large-n model, and generically it can be used to determine easily from simulations of coarsening models. We also argue that and the scaling function do not depend on temperature, leading to a definition of at finite temperature, whereas the local persistence probability decays exponentially due to thermal fluctuations. These ideas are applied to the study of persistence for conserved models. We illustrate our discussions by extensive numerical results. We also comment on the relation between this method and an alternative definition of at finite temperature recently introduced by Derrida [Phys. Rev. E 55, 3705 (1997)]. Received: 25 February 1998 / Revised: 24 July 1998 / Accepted: 27 July 1998     

Some comments on Kondo lattices and the Mott transition

The so called exhaustion problem occurs when few electrons have to screen many spins in a metal with magnetic impurities. A singlet Fermi liquid ground state is possible only if all impurities are “isotropized” in such a way as to suppress their entropy. That takes a time and the corresponding energy limits the Fermi liquid range. The present note explores that issue of time and energy scales, and it concludes that is much smaller than the single impurity Kondo temperature. Similarly the relevant energy scale is proportional to the number of electrons. Recent results on the Mott metal insulator transition in infinite dimension are reconsidered in the light of these results: controversies in that respect are shown to reduce to a simple physical question, with no firm answer as to now. Received: 5 May 1998 / Received in final form and Accepted: 29 July 1998     

Quantum localization observables and accelerated frames

We define quantum observables associated with Einstein localization in space-time. These observables are built on Poincaré and dilatation generators. Their commutators are given by spin observables defined from the same symmetry generators. Their shifts under transformations to uniformly accelerated frames are evaluated through algebraic computations in conformal algebra. Spin number is found to vary under such transformations with a variation involving further observables introduced as irreducible quadrupole momenta. Quadrupole observables may be dealt with as non commutative polarizations which allow one to define step operators increasing or decreasing the spin number by unity. Received: 11 December 1997 / Revised: 1st July 1998 / Accepted: 1st September 1998     

Canonically invariant formulation of Langevin and Fokker-Planck equations

We present a canonically invariant form for the generalized Langevin and Fokker-Planck equations. We discuss the role of constants of motion and the construction of conservative stochastic processes. Received : 24 July 1997 / Revised : 30 October 1997 / Accepted : 26 January 1998