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Title: Communication: Nucleation rates of supersaturated aqueous NaCl using a polarizable force field

Abstract

In this work, we use molecular dynamics simulations with a polarizable force field, namely, the modified AH/BK3 model [J. Kolafa, J. Chem. Phys. 145, 204509 (2016)], in combination with the forward flux sampling technique, to calculate the rates of homogeneous nucleation of NaCl from supersaturated aqueous solutions at 298 K and 1 bar. A non-polarizable model that reproduces the experimental equilibrium solubility {AH/TIP4P-2005 of Benavides et al. [J. Chem. Phys. 147, 104501 (2017)]} is also used for comparison. Nucleation rates calculated from the polarizable force field are found to be in good agreement with experimental measurements, while the non-polarizable model severely underestimates the nucleation rates. These results, in combination with our earlier study of a different non-polarizable force field [H. Jiang et al., J. Chem. Phys. 148, 044505 (2018)], lead to the conclusion that nucleation rates are sensitive to the details of force fields, and a good representation of nucleation rates may not be feasible using available non-polarizable force fields, even if these reproduce the equilibrium salt solubility. Finally, inclusion of polarization could be important for an accurate prediction of nucleation rates in salt solutions.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Princeton Univ., NJ (United States)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1610629
Alternate Identifier(s):
OSTI ID: 1476696
Grant/Contract Number:  
SC0002128; TG-CHE170059
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 14; 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; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chemistry; physics

Citation Formats

Jiang, Hao, Debenedetti, Pablo G., and Panagiotopoulos, Athanassios Z.. Communication: Nucleation rates of supersaturated aqueous NaCl using a polarizable force field. United States: N. p., 2018. Web. https://doi.org/10.1063/1.5053652.
Jiang, Hao, Debenedetti, Pablo G., & Panagiotopoulos, Athanassios Z.. Communication: Nucleation rates of supersaturated aqueous NaCl using a polarizable force field. United States. https://doi.org/10.1063/1.5053652
Jiang, Hao, Debenedetti, Pablo G., and Panagiotopoulos, Athanassios Z.. Mon . "Communication: Nucleation rates of supersaturated aqueous NaCl using a polarizable force field". United States. https://doi.org/10.1063/1.5053652. https://www.osti.gov/servlets/purl/1610629.
@article{osti_1610629,
title = {Communication: Nucleation rates of supersaturated aqueous NaCl using a polarizable force field},
author = {Jiang, Hao and Debenedetti, Pablo G. and Panagiotopoulos, Athanassios Z.},
abstractNote = {In this work, we use molecular dynamics simulations with a polarizable force field, namely, the modified AH/BK3 model [J. Kolafa, J. Chem. Phys. 145, 204509 (2016)], in combination with the forward flux sampling technique, to calculate the rates of homogeneous nucleation of NaCl from supersaturated aqueous solutions at 298 K and 1 bar. A non-polarizable model that reproduces the experimental equilibrium solubility {AH/TIP4P-2005 of Benavides et al. [J. Chem. Phys. 147, 104501 (2017)]} is also used for comparison. Nucleation rates calculated from the polarizable force field are found to be in good agreement with experimental measurements, while the non-polarizable model severely underestimates the nucleation rates. These results, in combination with our earlier study of a different non-polarizable force field [H. Jiang et al., J. Chem. Phys. 148, 044505 (2018)], lead to the conclusion that nucleation rates are sensitive to the details of force fields, and a good representation of nucleation rates may not be feasible using available non-polarizable force fields, even if these reproduce the equilibrium salt solubility. Finally, inclusion of polarization could be important for an accurate prediction of nucleation rates in salt solutions.},
doi = {10.1063/1.5053652},
journal = {Journal of Chemical Physics},
number = 14,
volume = 149,
place = {United States},
year = {2018},
month = {10}
}

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    Works referencing / citing this record:

    Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal
    journal, March 2019

    • Jiang, Hao; Debenedetti, Pablo G.; Panagiotopoulos, Athanassios Z.
    • The Journal of Chemical Physics, Vol. 150, Issue 12
    • DOI: 10.1063/1.5084248

    A force field of Li + , Na + , K + , Mg 2+ , Ca 2+ , Cl , and SO42− in aqueous solution based on the TIP4P/2005 water model and scaled charges for the ions
    journal, October 2019

    • Zeron, I. M.; Abascal, J. L. F.; Vega, C.
    • The Journal of Chemical Physics, Vol. 151, Issue 13
    • DOI: 10.1063/1.5121392

    Dynamic properties of aqueous electrolyte solutions from non-polarisable, polarisable, and scaled-charge models
    journal, August 2019