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ID 57454
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Author
Sumi, Tomonari Department of Chemistry, Okayama University ORCID Kaken ID publons researchmap
Sekino, Hideo Department of Computer Science and Engineering, Toyohashi University of Technology
Abstract
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.
Published Date
2013-05-07
Publication Title
RSC Advances
Volume
volume3
Issue
issue31
Publisher
Royal Society of Chemistry
Start Page
12743
End Page
12750
ISSN
20462069
Content Type
Journal Article
language
英語
OAI-PMH Set
岡山大学
File Version
publisher
DOI
Web of Science KeyUT
Related Url
isVersionOf https://doi.org/10.1039/C3RA41320A
Funder Name
Japan Society for the Promotion of Science