A cooperative phenomenon between polymer chain and supercritical solvent: Remarkable expansions of solvophobic and solvophilic polymers

Tomonari Sumi, Hideo Sekino

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26 Citations (Scopus)

Abstract

We propose a simulation method for infinitely dilute polymer solutions. In this method, an effective Hamiltonian of the solvated polymer chain is introduced to eliminate the degree of freedom of the solvent particle. The effective Hamiltonian is coupled with the density-functional theory (DFT) that we have developed for a polymer-solvent pair correlation function. All the equations proposed in this paper are derived from the first principle. This simulation method was applied to polymer chains in supercritical solvents. We observed anomalous behaviors of polymer chains near the liquid-vapor critical point: both solvophilic and solvophobic polymers expand significantly near the critical point; this is in contrast to the behavior of polymer chains in vacuum. This expansion can be interpreted as a cooperative phenomenon, which enhances the large long-wavelength density fluctuation of the solvent.

Original languageEnglish
Article number194910
JournalThe Journal of Chemical Physics
Volume122
Issue number19
DOIs
Publication statusPublished - May 15 2005
Externally publishedYes

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ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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