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Title: ReaxFF molecular dynamics simulation of intermolecular structure formation in acetic acid-water mixtures at elevated temperatures and pressures

Abstract

The intermolecular structure formation in liquid and supercritical acetic acid-water mixtures was explored using ReaxFF-based molecular dynamics simulations. The microscopic structures of acetic acid-water mixtures with different acetic acid mole fractions (1.0 ≥ x HAc ≥ 0.2) at ambient and critical conditions were examined. The potential energy surface associated with the dissociation of acetic acid molecules was calculated using a metadynamics procedure to optimize the dissociation energy of ReaxFF potential. At ambient conditions, depending on the acetic acid concentration, either acetic acid clusters or water clusters are dominant in the liquid mixture. When acetic acid is dominant (0.4 ≤ x HAc), cyclic dimers and chain structures between acetic acid molecules are present in the mixture. Both structures disappear at increased water content of the mixture. It was found by simulations that the acetic acid molecules released from these dimer and chain structures tend to stay in a dipole-dipole interaction. These structural changes are in agreement with the experimental findings. When switched to critical conditions, the long-range interactions (e.g., second or fourth neighbor) disappear and the water-water and acetic acid-acetic acid structural formations become disordered. The simulated radial distribution function for water-water interactions is in agreement with experimental and computational studies.more » The first neighbor interactions between acetic acid and water molecules are preserved at relatively lower temperatures of the critical region. As higher temperatures are reached in the critical region, these interactions were observed to weaken. These simulations suggest that ReaxFF molecular dynamics simulations are an appropriate tool for studying supercritical water/organic acid mixtures.« less

Authors:
 [1]; ORCiD logo [1];  [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1540186
Alternate Identifier(s):
OSTI ID: 1435001
Grant/Contract Number:  
AR0000766
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sengul, Mert Y., Randall, Clive A., and van Duin, Adri C. T. ReaxFF molecular dynamics simulation of intermolecular structure formation in acetic acid-water mixtures at elevated temperatures and pressures. United States: N. p., 2018. Web. doi:10.1063/1.5025932.
Sengul, Mert Y., Randall, Clive A., & van Duin, Adri C. T. ReaxFF molecular dynamics simulation of intermolecular structure formation in acetic acid-water mixtures at elevated temperatures and pressures. United States. doi:10.1063/1.5025932.
Sengul, Mert Y., Randall, Clive A., and van Duin, Adri C. T. Fri . "ReaxFF molecular dynamics simulation of intermolecular structure formation in acetic acid-water mixtures at elevated temperatures and pressures". United States. doi:10.1063/1.5025932. https://www.osti.gov/servlets/purl/1540186.
@article{osti_1540186,
title = {ReaxFF molecular dynamics simulation of intermolecular structure formation in acetic acid-water mixtures at elevated temperatures and pressures},
author = {Sengul, Mert Y. and Randall, Clive A. and van Duin, Adri C. T.},
abstractNote = {The intermolecular structure formation in liquid and supercritical acetic acid-water mixtures was explored using ReaxFF-based molecular dynamics simulations. The microscopic structures of acetic acid-water mixtures with different acetic acid mole fractions (1.0 ≥ xHAc ≥ 0.2) at ambient and critical conditions were examined. The potential energy surface associated with the dissociation of acetic acid molecules was calculated using a metadynamics procedure to optimize the dissociation energy of ReaxFF potential. At ambient conditions, depending on the acetic acid concentration, either acetic acid clusters or water clusters are dominant in the liquid mixture. When acetic acid is dominant (0.4 ≤ xHAc), cyclic dimers and chain structures between acetic acid molecules are present in the mixture. Both structures disappear at increased water content of the mixture. It was found by simulations that the acetic acid molecules released from these dimer and chain structures tend to stay in a dipole-dipole interaction. These structural changes are in agreement with the experimental findings. When switched to critical conditions, the long-range interactions (e.g., second or fourth neighbor) disappear and the water-water and acetic acid-acetic acid structural formations become disordered. The simulated radial distribution function for water-water interactions is in agreement with experimental and computational studies. The first neighbor interactions between acetic acid and water molecules are preserved at relatively lower temperatures of the critical region. As higher temperatures are reached in the critical region, these interactions were observed to weaken. These simulations suggest that ReaxFF molecular dynamics simulations are an appropriate tool for studying supercritical water/organic acid mixtures.},
doi = {10.1063/1.5025932},
journal = {Journal of Chemical Physics},
number = 16,
volume = 148,
place = {United States},
year = {2018},
month = {4}
}

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Works referenced in this record:

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Molecular Simulations of Liquid and Supercritical Water: Thermodynamics, Structure, and Hydrogen Bonding
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Demonstration of the cold sintering process study for the densification and grain growth of ZnO ceramics
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Exploring the conformational and reactive dynamics of biomolecules in solution using an extended version of the glycine reactive force field
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    Works referencing / citing this record:

    Reactions at supercritical conditions: Applications and fundamentals
    journal, July 1995

    • Savage, Phillip E.; Gopalan, Sudhama; Mizan, Thamid I.
    • AIChE Journal, Vol. 41, Issue 7
    • DOI: 10.1002/aic.690410712

    The structure of liquid acetic acid-an interpretation of neutron diffraction results by geometrical models
    journal, December 1982


    VMD: Visual molecular dynamics
    journal, February 1996


    The critical temperatures and densities of acetic acidwater mixtures
    journal, January 1995


    Universality of hydrogen bond distributions in liquid and supercritical water
    journal, September 2017


    Effect of acetic acid on ZnO:In transparent conductive oxide prepared by ultrasonic spray pyrolysis
    journal, December 2011


    Ultrafast vibrational dynamics of doubly hydrogen bonded acetic acid dimers in liquid solution
    journal, January 2001


    Second-Generation ReaxFF Water Force Field: Improvements in the Description of Water Density and OH-Anion Diffusion
    journal, June 2017

    • Zhang, Weiwei; van Duin, Adri C. T.
    • The Journal of Physical Chemistry B, Vol. 121, Issue 24
    • DOI: 10.1021/acs.jpcb.7b02548

    Low-frequency Raman spectra and molecular association in liquid formic and acetic acids
    journal, June 1967

    • Waldstein, Peter; Blatz, Lawrence A.
    • The Journal of Physical Chemistry, Vol. 71, Issue 7
    • DOI: 10.1021/j100866a047

    Solvent Effects on Hydrogen BondsA Theoretical Study
    journal, March 2002

    • Aquino, Adélia J. A.; Tunega, Daniel; Haberhauer, Georg
    • The Journal of Physical Chemistry A, Vol. 106, Issue 9
    • DOI: 10.1021/jp013677x

    Acetic Acid Dimer in the Gas Phase, Nonpolar Solvent, Microhydrated Environment, and Dilute and Concentrated Acetic Acid:  Ab Initio Quantum Chemical and Molecular Dynamics Simulations
    journal, May 2003

    • Chocholoušová, Jana; Vacek, Jaroslav; Hobza, Pavel
    • The Journal of Physical Chemistry A, Vol. 107, Issue 17
    • DOI: 10.1021/jp027637k

    Liquid Structure of Acetic Acid−Water and Trifluoroacetic Acid−Water Mixtures Studied by Large-Angle X-ray Scattering and NMR
    journal, August 2007

    • Takamuku, Toshiyuki; Kyoshoin, Yasuhiro; Noguchi, Hiroshi
    • The Journal of Physical Chemistry B, Vol. 111, Issue 31
    • DOI: 10.1021/jp0724976

    Computer Simulations on Aggregation of Acetic Acid in the Gas Phase, Liquid Phase, and Supercritical Carbon Dioxide
    journal, April 2010

    • Xu, Wenhao; Yang, Jichu
    • The Journal of Physical Chemistry A, Vol. 114, Issue 16
    • DOI: 10.1021/jp100040j

    Dissociation Constants of Weak Acids from ab Initio Molecular Dynamics Using Metadynamics: Influence of the Inductive Effect and Hydrogen Bonding on p K a Values
    journal, September 2014

    • Tummanapelli, Anil Kumar; Vasudevan, Sukumaran
    • The Journal of Physical Chemistry B, Vol. 118, Issue 47
    • DOI: 10.1021/jp5088898

    Hydrogen Bonding in Supercritical Water. 2. Computer Simulations
    journal, December 1997

    • Kalinichev, A. G.; Bass, J. D.
    • The Journal of Physical Chemistry A, Vol. 101, Issue 50
    • DOI: 10.1021/jp971218j

    Liquid Structure of Acetic Acid Studied by Raman Spectroscopy and Ab Initio Molecular Orbital Calculations
    journal, October 1999

    • Nakabayashi, Takakazu; Kosugi, Kentaroh; Nishi, Nobuyuki
    • The Journal of Physical Chemistry A, Vol. 103, Issue 43
    • DOI: 10.1021/jp991501d

    The ReaxFF reactive force-field: development, applications and future directions
    journal, March 2016


    Ab initio study of the vibrational properties of acetic acid monomers and dimers
    journal, January 2000

    • Burneau, Andre´; Ge´nin, Francine; Quilès, Fabienne
    • Physical Chemistry Chemical Physics, Vol. 2, Issue 22
    • DOI: 10.1039/b006230h

    Exploring the conformational and reactive dynamics of biomolecules in solution using an extended version of the glycine reactive force field
    journal, January 2013

    • Monti, Susanna; Corozzi, Alessandro; Fristrup, Peter
    • Physical Chemistry Chemical Physics, Vol. 15, Issue 36
    • DOI: 10.1039/c3cp51931g

    Molecular dynamics with coupling to an external bath
    journal, October 1984

    • Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
    • The Journal of Chemical Physics, Vol. 81, Issue 8
    • DOI: 10.1063/1.448118

    Analysis of the hydrogen bonding and vibrational spectra of supercritical model water by molecular dynamics simulations
    journal, April 1999

    • Martı́, J.
    • The Journal of Chemical Physics, Vol. 110, Issue 14
    • DOI: 10.1063/1.478593

    Microscopic structure of water at elevated pressures and temperatures
    journal, March 2013

    • Sahle, C. J.; Sternemann, C.; Schmidt, C.
    • Proceedings of the National Academy of Sciences, Vol. 110, Issue 16
    • DOI: 10.1073/pnas.1220301110

    Escaping free-energy minima
    journal, September 2002

    • Laio, A.; Parrinello, M.
    • Proceedings of the National Academy of Sciences, Vol. 99, Issue 20
    • DOI: 10.1073/pnas.202427399

    Effective carbon number molecular weight carbon number Pressure Temperature
    journal, November 1987


    Hydrogen bond studies. XLIV. Neutron diffraction study of acetic acid
    journal, May 1971

    • Jönsson, P. G.
    • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 27, Issue 5
    • DOI: 10.1107/s0567740871003224

    Demonstration of the cold sintering process study for the densification and grain growth of ZnO ceramics
    journal, October 2016

    • Funahashi, Shuichi; Guo, Jing; Guo, Hanzheng
    • Journal of the American Ceramic Society, Vol. 100, Issue 2
    • DOI: 10.1111/jace.14617

    Structure of hydrogen-bonded associates in supercritical water under low and high pressures
    journal, February 2013

    • Antipova, M. L.; Gurina, D. L.; Petrenko, V. E.
    • Russian Journal of Physical Chemistry A, Vol. 87, Issue 3
    • DOI: 10.1134/s0036024413030035

    Molecular Simulations of Liquid and Supercritical Water: Thermodynamics, Structure, and Hydrogen Bonding
    journal, January 2001


    Hydrogen Bond Studies. 39. Reinvestigation of the Crystal Structure of Acetic Acid (at +5 degrees C and -190 degrees C).
    journal, January 1970