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Title: Perfluoropolyethers: Development of an All-Atom Force Field for Molecular Simulations and Validation with New Experimental Vapor Pressures and Liquid Densities

Abstract

A force field for perfluoropolyethers (PFPEs) based on the general optimized potentials for liquid simulations all-atom (OPLS-AA) force field has been derived in conjunction with experiments and ab initio quantum mechanical calculations. Vapor pressures and densities of two liquid PFPEs, perfluorodiglyme (CF3–O–(CF2–CF2–O)2–CF3) and perfluorotriglyme (CF3–O–(CF2–CF2–O)3–CF3), have been measured experimentally to validate the force field and increase our understanding of the physical properties of PFPEs. Force field parameters build upon those for related molecules (e.g., ethers and perfluoroalkanes) in the OPLS-AA force field, with new parameters introduced for interactions specific to PFPEs. Molecular dynamics simulations using the new force field demonstrate excellent agreement with ab initio calculations at the RHF/6-31G* level for gas-phase torsional energies (<0.5 kcal mol–1 error) and molecular structures for several PFPEs, and also accurately reproduce experimentally determined densities (<0.02 g cm–3 error) and enthalpies of vaporization derived from experimental vapor pressures (<0.3 kcal mol–1). Additional comparisons between experiment and simulation show that polyethers demonstrate a significant decrease in enthalpy of vaporization upon fluorination unlike related molecules (e.g., alkanes and alcohols). Simulation suggests this phenomenon is a result of reduced cohesion in liquid PFPEs due to a reduction in localized associations between backbone oxygen atoms and neighboring molecules.

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [4]
  1. Vanderbilt Univ., Nashville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Vanderbilt Univ., Nashville, TN (United States). Multiscale Modeling and Simulation (MuMS)
  2. Univ. de Lisboa, Lisboa (Portugal). Centro de Química Estrutural, Inst. Superior Técnico
  3. Univ. de Lisboa, Lisboa (Portugal). Centro de Química Estrutural, Inst. Superior Técnico; Univ. de Évora, Évora (Portugal). Centro de Química de Évora
  4. Vanderbilt Univ., Nashville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Vanderbilt Univ., Nashville, TN (United States). Multiscale Modeling and Simulation (MuMS); Vanderbilt Univ., Nashville, TN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC); US Dept. of Education
OSTI Identifier:
1480285
Grant/Contract Number:  
AC02-05CH11231; ACI-1047828; ACI-1535150; P200A090323; UID/QUI/0100/2013; SFRH/BPD/81748/2011; PEst-OE/QUI/UI0619/2011
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 27; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Black, Jana E., Silva, Gonçalo M. C., Klein, Christoph, Iacovella, Christopher R., Morgado, Pedro, Martins, Luís F. G., Filipe, Eduardo J. M., and McCabe, Clare. Perfluoropolyethers: Development of an All-Atom Force Field for Molecular Simulations and Validation with New Experimental Vapor Pressures and Liquid Densities. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcb.7b00891.
Black, Jana E., Silva, Gonçalo M. C., Klein, Christoph, Iacovella, Christopher R., Morgado, Pedro, Martins, Luís F. G., Filipe, Eduardo J. M., & McCabe, Clare. Perfluoropolyethers: Development of an All-Atom Force Field for Molecular Simulations and Validation with New Experimental Vapor Pressures and Liquid Densities. United States. https://doi.org/10.1021/acs.jpcb.7b00891
Black, Jana E., Silva, Gonçalo M. C., Klein, Christoph, Iacovella, Christopher R., Morgado, Pedro, Martins, Luís F. G., Filipe, Eduardo J. M., and McCabe, Clare. Tue . "Perfluoropolyethers: Development of an All-Atom Force Field for Molecular Simulations and Validation with New Experimental Vapor Pressures and Liquid Densities". United States. https://doi.org/10.1021/acs.jpcb.7b00891. https://www.osti.gov/servlets/purl/1480285.
@article{osti_1480285,
title = {Perfluoropolyethers: Development of an All-Atom Force Field for Molecular Simulations and Validation with New Experimental Vapor Pressures and Liquid Densities},
author = {Black, Jana E. and Silva, Gonçalo M. C. and Klein, Christoph and Iacovella, Christopher R. and Morgado, Pedro and Martins, Luís F. G. and Filipe, Eduardo J. M. and McCabe, Clare},
abstractNote = {A force field for perfluoropolyethers (PFPEs) based on the general optimized potentials for liquid simulations all-atom (OPLS-AA) force field has been derived in conjunction with experiments and ab initio quantum mechanical calculations. Vapor pressures and densities of two liquid PFPEs, perfluorodiglyme (CF3–O–(CF2–CF2–O)2–CF3) and perfluorotriglyme (CF3–O–(CF2–CF2–O)3–CF3), have been measured experimentally to validate the force field and increase our understanding of the physical properties of PFPEs. Force field parameters build upon those for related molecules (e.g., ethers and perfluoroalkanes) in the OPLS-AA force field, with new parameters introduced for interactions specific to PFPEs. Molecular dynamics simulations using the new force field demonstrate excellent agreement with ab initio calculations at the RHF/6-31G* level for gas-phase torsional energies (<0.5 kcal mol–1 error) and molecular structures for several PFPEs, and also accurately reproduce experimentally determined densities (<0.02 g cm–3 error) and enthalpies of vaporization derived from experimental vapor pressures (<0.3 kcal mol–1). Additional comparisons between experiment and simulation show that polyethers demonstrate a significant decrease in enthalpy of vaporization upon fluorination unlike related molecules (e.g., alkanes and alcohols). Simulation suggests this phenomenon is a result of reduced cohesion in liquid PFPEs due to a reduction in localized associations between backbone oxygen atoms and neighboring molecules.},
doi = {10.1021/acs.jpcb.7b00891},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 27,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}

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