Effects of hydrophobic hydration on polymer chains immersed in supercooled water

Tomonari Sumi, Hideo Sekino

Research output: Contribution to journalArticlepeer-review

49 Citations (Scopus)


A multiscale simulation of a hydrophobic polymer chain immersed in water including the supercooled region is presented. Solvent effects on the polymer conformation were taken into account via liquid-state density functional theory in which a free-energy functional model was constructed using a density response function of bulk water, determined from a molecular dynamics (MD) simulation. This approach overcomes sampling problems in simulations of high-viscosity polymer solutions in the deeply supercooled region. Isobars determined from the MD simulations of 4000 water molecules suggest a liquid-liquid transition in the deeply supercooled region. The multiscale simulation reveals that a hydrophobic polymer chain exhibits swelling upon cooling along isobars below a hypothesized second critical pressure; no remarkable swelling is observed at higher pressures. These observations agree with the behavior of a polymer chain in a Jagla solvent model that qualitatively reproduces the thermodynamics and dynamics of liquid water. A theoretical analysis of the results obtained from the multiscale simulation show that a decrease in entropy due to the swelling arises from the formation of a tetrahedral hydrogen bond network in the hydration shell.

Original languageEnglish
Pages (from-to)12743-12750
Number of pages8
JournalRSC Advances
Issue number31
Publication statusPublished - Aug 21 2013

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering


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