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Title: Molecular driving forces behind the tetrahydrofuran–water miscibility gap

Abstract

The tetrahydrofuran water binary system exhibits an unusual closed-loop miscibility gap (transitions from a miscible regime to an immiscible regime back to another miscible regime as the temperature increases). Here, using all-atom molecular dynamics simulations, we probe the structural and dynamical behavior of the binary system in the temperature regime of this gap at four different mass ratios, and we compare the behavior of bulk water and tetrahydrofuran. The changes in structure and dynamics observed in the simulations indicate that the temperature region associated with the miscibility gap is distinctive. Within the miscibility-gap temperature region, the self diffusion of water is significantly altered and the second virial coefficients (pair interaction strengths) show parabolic-like behavior. Altogether, the results suggest that the gap is the result of differing trends with temperature of minor structural changes, which produces interaction virials with parabolic temperature dependence near the miscibility gap.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1327650
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 120; Journal Issue: 4; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Smith, Micholas Dean, Mostofian, Barmak, Petridis, Loukas, Cheng, Xiaolin, and Smith, Jeremy C. Molecular driving forces behind the tetrahydrofuran–water miscibility gap. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.5b09770.
Smith, Micholas Dean, Mostofian, Barmak, Petridis, Loukas, Cheng, Xiaolin, & Smith, Jeremy C. Molecular driving forces behind the tetrahydrofuran–water miscibility gap. United States. https://doi.org/10.1021/acs.jpcb.5b09770
Smith, Micholas Dean, Mostofian, Barmak, Petridis, Loukas, Cheng, Xiaolin, and Smith, Jeremy C. Wed . "Molecular driving forces behind the tetrahydrofuran–water miscibility gap". United States. https://doi.org/10.1021/acs.jpcb.5b09770. https://www.osti.gov/servlets/purl/1327650.
@article{osti_1327650,
title = {Molecular driving forces behind the tetrahydrofuran–water miscibility gap},
author = {Smith, Micholas Dean and Mostofian, Barmak and Petridis, Loukas and Cheng, Xiaolin and Smith, Jeremy C.},
abstractNote = {The tetrahydrofuran water binary system exhibits an unusual closed-loop miscibility gap (transitions from a miscible regime to an immiscible regime back to another miscible regime as the temperature increases). Here, using all-atom molecular dynamics simulations, we probe the structural and dynamical behavior of the binary system in the temperature regime of this gap at four different mass ratios, and we compare the behavior of bulk water and tetrahydrofuran. The changes in structure and dynamics observed in the simulations indicate that the temperature region associated with the miscibility gap is distinctive. Within the miscibility-gap temperature region, the self diffusion of water is significantly altered and the second virial coefficients (pair interaction strengths) show parabolic-like behavior. Altogether, the results suggest that the gap is the result of differing trends with temperature of minor structural changes, which produces interaction virials with parabolic temperature dependence near the miscibility gap.},
doi = {10.1021/acs.jpcb.5b09770},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 4,
volume = 120,
place = {United States},
year = {2016},
month = {1}
}

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