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.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry