Mean field theory for the intermolecular and intramolecular conformational transitions of a single flexible polyelectrolyte chain

Chwen-Yang Shew; Yoshikawa, Kenichi
April 2007
Journal of Chemical Physics;4/14/2007, Vol. 126 Issue 14, p144913
Academic Journal
The diMarzio theory has been extended to elucidate the intermolecular and intramolecular phase segregations of a single flexible chain polyelectrolyte in dilute salt-free solutions. At the long chain limit, this theory yields the formalism obtained from the more sophisticated Edward Hamiltonian for polyelectrolyte problems. The calculated phase diagram exhibits the features of a first-order phase transition, with continuous and discontinuous transitions separated by a critical point. Under the discontinuous transition, the polyelectrolyte chain exhibits coexistent expanded and collapsed conformational states, same as intermolecular phase segregation. For a limiting long chain, the mean chain size at critical point is roughly 90% of the size of an ideal chain. Such a result implies that partial contraction within a chain molecule is required to collapse a flexible polyelectrolyte chain. Moreover, the theory predicts that for a longer chain, intramolecular segregated conformations differ significantly from intermolecular segregated conformations, but the difference becomes small for shorter chains. Besides, the charge needed to induce intramolecular segregation is smaller than that of intermolecular segregation for a given chain length. These findings are consistent with previous literature results.


Related Articles

  • Segmental relaxation in semicrystalline polymers: A mean-field model for the distribution of relaxation times in confined regimes. Pieruccini, M.; Ezquerra, T.A. // European Physical Journal E -- Soft Matter;Jun2009, Vol. 29 Issue 2, p163 

    The effect of confinement in the segmental relaxation of polymers is considered. On the basis of a thermodynamic model we discuss the emerging relevance of the fast degrees of freedom in stimulating the much slower segmental relaxation, as an effect of the constraints at the walls of the...

  • More is the Same; Phase Transitions and Mean Field Theories. Kadanoff, Leo P. // Journal of Statistical Physics;Dec2009, Vol. 137 Issue 5/6, p777 

    This paper is the first in a series that will look at the theory of phase transitions from the perspectives of physics and the philosophy of science. The series will consider a group of related concepts derived from condensed matter and statistical physics. The key technical ideas go under the...

  • Crossover Critical Behavior in the Three-Dimensional Ising Model. Kim, Young C.; Anisimov, Mikhail A.; Sengers, Jan V.; Luijten, Erik // Journal of Statistical Physics;Mar2003, Vol. 110 Issue 3-6, p591 

    The character of critical behavior in physical systems depends on the range of interactions. In the limit of infinite range of the interactions, systems will exhibit mean-field critical behavior, i.e., critical behavior not affected by fluctuations of the order parameter. If the interaction...

  • Relativistic Description of Exotic Nuclei and Nuclear Matter at Extreme Conditions. Meng, J.; Ban, S. F.; Li, J.; Long, W. H.; Lü, H. F.; Zhang, S. Q.; Zhang, W.; Zhou, S.-G. // Physics of Atomic Nuclei;Sep2004, Vol. 67 Issue 9, p1619 

    Recent works on the relativistic description of exotic nuclei and nuclear matter at extreme conditions are reviewed. New parameter sets for the Lagrangian density in the relativistic mean field (RMF) theory, PK1, PK1r, and PKDD are proposed with the center-of-mass correction included in a...

  • The Time Evolution of Fluctuation Algebra in Mean Field Theories. Narnhofer, Heide // Foundations of Physics Letters;Jun2004, Vol. 17 Issue 3, p235 

    Fluctuation algebra is defined for equilibrium states of mean field theories. The time evolution is calculated; and, in contrast to interactions with finite range, the fluctuation algebra is not in a KMS state with respect to this time evolution though the underlying quasilocal state. If the...

  • Theoretical simulation for identical bands. Chen, Y. J.; Chen, Y.S.; Shen, C. W.; Gao, Z. C.; Zhu, S. J.; Tu, Y. // European Physical Journal A -- Hadrons & Nuclei;May2005, Vol. 24 Issue 2, p185 

    The frequency of occurrence of identical bands in superdeformed and normal-deformed nuclei is studied by carrying out a statistical analysis of a large number of rotational bands, which are generated with the reflection asymmetric shell model. The frequency of occurrence and the behaviors of...

  • Shape evolution for Sm isotopes in relativistic mean-field theory. Meng, J.; Zhang, W.; Zhou, S.; Toki, H.; Geng, L. // European Physical Journal A -- Hadrons & Nuclei;Jul2005, Vol. 25 Issue 1, p23 

    The evolution of shape from the spherical to the axially deformed shapes in the Sm isotopes is investigated microscopically in relativistic mean-field theory. The microscopic and self-consistent quadrupole deformation constrained relativistic mean-field calculations show a clear shape change for...

  • Gravitational clustering: an overview. Labini, Francesco Sylos // AIP Conference Proceedings;1/11/2008, Vol. 970 Issue 1, p205 

    We discuss the differences and analogies of gravitational clustering in finite and infinite systems. The process of collective, or violent, relaxation leading to the formation of quasi-stationary states is one of the distinguished features in the dynamics of self-gravitating systems. This...

  • Nuclear Ground-State Observables from Relativistic Mean-Field Models: Masses, Densities, Radii, Single-Particle Levels. Buervenich, T. J.; Madland, D. G. // AIP Conference Proceedings;2005, Vol. 769 Issue 1, p1140 

    We report on the current status of relativistic mean-field models for the calculation and prediction of nuclear ground-state observables. These models are quite powerful and can be applied to light (A >= 16), medium, and heavy nuclei (spherical and deformed) and allow realistic extrapolations to...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics