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On the elasticity of a single polyelectrolyte chain

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 Added by J. Wilder
 Publication date 1997
  fields Physics
and research's language is English




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This paper discusses the elastic behavior of a single polyelectrolyte chain. A simple scaling analysis as in self avoiding walk chains are not possible, because three interplaying relevant length scales are involved, i.e., the Debye screening length and the Pincus blob size. Therefore a selfconsistent computation of an effective variational propagator is employed. It is shown that the elastic force f is proportional to the end to end distance R for small f. For larger forces we find a new regime, characterized by deformations larger than a computed electrostatic blob size. These results are supported by simulations and intuitive physical arguments.



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341 - J. Wilder , T. A. Vilgis 1997
This paper discusses the elastic behavior of a very long crosslinked polyelectrolyte chain (Debye-Huckel chain), which is weakly charged. Therefore the response of the crosslinked chain (network) on an external constant force $f$ acting on the ends of the chain is considered. A selfconsistent variational computation of an effective field theory is employed. It is shown, that the modulus of the polyelectrolyte network has two parts: the first term represents the usual entropy elasticity of connected flexible chains and the second term takes into account the electrostatic interaction of the monomers. It is proportional to the squared crosslink density and the Debye - screening parameter.
212 - B.-Y. Ha , D. Thirumalai 1998
We calculate the dependence of the electrostatic persistence length, l_e, of weakly charged flexible polyelectrolyte chains using a self-consistent variational theory. The variation of l_e with kappa, the inverse Debye screening length, is controlled by the parameter l_0 l_B/A^2, where l_0 is the bare persistence length, l_B is the Bjerrum length, and A is the mean distance between charges along the chain. Several distinct regimes for the dependence of l_e on kappa emerge depending on the value of l_0 l_B/A^2. We show that when l_0 l_B /A^2 << 1 we recover the classical result, l_e propto kappa^{-2}. For intermediate values of l_0 l_B /A^2, l_e propto kappa^{-1}. In this regime one can also get l_e propto kappa^{-y} with y < 1 depending on the strength of the Coulomb interaction. Qualitative comparisons between our theory and simulations as well as other theories are presented.
70 - T.A. Vilgis , J. Wilder 1997
This paper discusses the elastic behavior of polyelectrolyte networks. The deformation behavior of single polyelectrolyte chains is discussed. It is shown that a strong coupling between interactions and chain elasticity exists. The theory of the complete crosslinked networks shows that the Flory - Rehner - Hypothesis (FRH) does not hold. The modulus contains contributions from the classical rubber elasticity and from the electrostatic interactions. The equilibrium degree of swelling is estimated by the assumption of a $c^{*}$-network.
Due to their unique structural and mechanical properties, randomly-crosslinked polymer networks play an important role in many different fields, ranging from cellular biology to industrial processes. In order to elucidate how these properties are controlled by the physical details of the network (textit{e.g.} chain-length and end-to-end distributions), we generate disordered phantom networks with different crosslinker concentrations $C$ and initial density $rho_{rm init}$ and evaluate their elastic properties. We find that the shear modulus computed at the same strand concentration for networks with the same $C$, which determines the number of chains and the chain-length distribution, depends strongly on the preparation protocol of the network, here controlled by $rho_{rm init}$. We rationalise this dependence by employing a generic stress-strain relation for polymer networks that does not rely on the specific form of the polymer end-to-end distance distribution. We find that the shear modulus of the networks is a non-monotonic function of the density of elastically-active strands, and that this behaviour has a purely entropic origin. Our results show that if short chains are abundant, as it is always the case for randomly-crosslinked polymer networks, the knowledge of the exact chain conformation distribution is essential for predicting correctly the elastic properties. Finally, we apply our theoretical approach to published experimental data, qualitatively confirming our interpretations.
390 - D. Braak , N. Andrei 2001
In a recent paper (cond-mat/0009279), Fabricius and McCoy studied the spectrum of the spin 1/2 XXZ-model at Delta = (q+q^{-1})/2 and q^{2N}=1 for integer N >1. They found a certain pattern of degeneracies and linked it to the sl(2)-loop symmetry present in the commensurable spin sector (N divides S^z). We show that the degeneracies are due to zero-energy, transparent excitations, the cyclic bound states. These exist both in commensurable and incommensurable sectors, indicating a symmetry, of which sl(2)-loop is a partial manifestation. Our approach treats both sectors on even footing and yields an analytical expression for the degeneracies in the case N = 3.
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