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The quantum mechanics-based polarizable force field for water simulations

Naserifar, Saber and Goddard, William A., III (2018) The quantum mechanics-based polarizable force field for water simulations. Journal of Chemical Physics, 149 (17). Art. No. 174502. ISSN 0021-9606.

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We report here a new force field for water based solely on quantum mechanics (QM) calculations with no empirical data. The QM was at a high level, coupled cluster single double triple, for all orientations and distances for water dimer plus X3LYP density functional theory (DFT) on 19 larger water clusters. In addition, we included charge and polarization based on the polarizable charge equilibration method and nonbond interactions from DFT-D3 calculations on the H_2 and O_2 crystal. This model, denoted as RexPoN, provides quite excellent agreement with experimental (expr) data for the solid and liquid phase of water: T_(melt) = 273.3 K (expr = 273.15 K) and properties at 298 K: ΔH_(vap) = 10.36 kcal/mol (expr = 10.52), density = 0.9965 gr/cm^3 (expr = 0.9965), entropy = 68.4 (J/mol)/K (expr = 69.9), dielectric constant = 76.1 (expr = 78.4), and ln D_s (self-diffusion coef) = −10.08 (expr = −11.24). Such an accurate force field for water will, we believe, be useful for full solvent calculations of electrocatalysis, where we can restrict QM water to just the first one or two layers involving reactions, using RexPoN to provide the polarization for a more distant solvent. Also, RexPoN may provide a better description of the solvent for proteins, DNA, polymers, and inorganic systems for applications to biomolecular, pharma, electrocatalysis (fuel cells and water splitting), and batteries where interaction with explicit water molecules plays a significant role.

Item Type:Article
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URLURL TypeDescription Material
Naserifar, Saber0000-0002-1069-9789
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2018 Published by AIP Publishing. Accepted: September 2018. Published Online: 06 November 2018. This work was supported by the Computational Materials Sciences Program funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC00014607. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation Grant No. ACI-1548562. W.A.G. was supported by NSF (CBET 1512759).
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Department of Energy (DOE)DE-SC00014607
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Issue or Number:17
Record Number:CaltechAUTHORS:20181107-142156245
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90723
Deposited By: Donna Wrublewski
Deposited On:07 Nov 2018 22:55
Last Modified:05 Nov 2019 17:43

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