TY - JOUR
T1 - Communication
T2 - Nucleation rates of supersaturated aqueous NaCl using a polarizable force field
AU - Jiang, Hao
AU - Debenedetti, Pablo G.
AU - Panagiotopoulos, Athanassios Z.
N1 - Funding Information:
Financial support for this work was provided by the Office of Basic Energy Sciences, U.S. Department of Energy, under Award No. DE-SC0002128. Additional support was provided by the National Oceanic and Atmospheric Administration (Cooperative Institute for Climate Science Award No. AWD 1004131) and the U.S. National Science Foundation under Award No. CBET-1402166. We would like to thank Professor Amir Haji-Akbari for helpful discussion on FFS with jumpy order parameters. Calculations are performed on the Terascale Infrastructure for Groundbreaking Research in the Engineering and Science (TIGRESS) computing facility at Princeton University. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation Grant No. TG-CHE170059.
Publisher Copyright:
© 2018 Author(s).
PY - 2018/10/14
Y1 - 2018/10/14
N2 - 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. Inclusion of polarization could be important for an accurate prediction of nucleation rates in salt solutions.
AB - 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. Inclusion of polarization could be important for an accurate prediction of nucleation rates in salt solutions.
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U2 - 10.1063/1.5053652
DO - 10.1063/1.5053652
M3 - Article
C2 - 30316274
AN - SCOPUS:85054812248
SN - 0021-9606
VL - 149
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 14
M1 - 141102
ER -