Self-consistent polymer integral equation theory: Comparisons with Monte Carlo simulations and alternative closure approximations

Arun Yethiraj, Kenneth S Schweizer

Research output: Contribution to journalReview article

Abstract

Recently, Schweizer, Honnell, and Curro reported a self-consistent formulation of the polymer reference interaction site model (PRISM) theory for polymer melts. The purpose of this paper is to compare the predictions of this theory to Monte Carlo simulations of hard chains thereby allowing an independent test of the various approximations in the PRISM theory. We find that the self-consistent PRISM theory with the Percus-Yevick (PY) closure is very accurate for both the intramolecular and intermolecular correlations in hard 20-mers for a wide range of densities. The accuracy of the theory for longer chains is somewhat diminished. We also compare the PRISM theory predictions using the PY, hypernetted chain (HNC), and Martynov-Sarkisov (MS) atomiclike closures. All the closures give equally good predictions at high densities, but the HNC and MS closures exhibit unphysical features, and ultimately fail to converge, at lower densities and/or large chain lengths.

Original languageEnglish (US)
Pages (from-to)1455-1464
Number of pages10
JournalThe Journal of chemical physics
Volume97
Issue number2
StatePublished - 1992

Fingerprint

closures
Integral equations
integral equations
Polymers
polymers
approximation
simulation
Signal filtering and prediction
predictions
Polymer melts
interactions
Chain length
Monte Carlo simulation
formulations

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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abstract = "Recently, Schweizer, Honnell, and Curro reported a self-consistent formulation of the polymer reference interaction site model (PRISM) theory for polymer melts. The purpose of this paper is to compare the predictions of this theory to Monte Carlo simulations of hard chains thereby allowing an independent test of the various approximations in the PRISM theory. We find that the self-consistent PRISM theory with the Percus-Yevick (PY) closure is very accurate for both the intramolecular and intermolecular correlations in hard 20-mers for a wide range of densities. The accuracy of the theory for longer chains is somewhat diminished. We also compare the PRISM theory predictions using the PY, hypernetted chain (HNC), and Martynov-Sarkisov (MS) atomiclike closures. All the closures give equally good predictions at high densities, but the HNC and MS closures exhibit unphysical features, and ultimately fail to converge, at lower densities and/or large chain lengths.",
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