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Title: Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion

Abstract

Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li+ to PC from water, based on electronic structure calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li+/PF6- transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial chargesmore » in simple, nonpolarizable force fields in future studies of these electrolyte solutions.« less

Authors:
 [1];  [2];  [3];  [4];  [4];  [1]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Politecnico di Torino, Turin (Italy)
  3. Tulane Univ., New Orleans, LA (United States)
  4. Texas A & M Univ., College Station, TX (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1339276
Report Number(s):
SAND-2017-0023J
Journal ID: ISSN 1549-9618; 650174
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 12; Journal Issue: 12; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chaudhari, Mangesh I., Nair, Jijeesh R., Pratt, Lawrence R., Soto, Fernando A., Balbuena, Perla B., and Rempe, Susan B. Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion. United States: N. p., 2016. Web. doi:10.1021/acs.jctc.6b00824.
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Chaudhari, Mangesh I., Nair, Jijeesh R., Pratt, Lawrence R., Soto, Fernando A., Balbuena, Perla B., & Rempe, Susan B. Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion. United States. https://doi.org/10.1021/acs.jctc.6b00824
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Chaudhari, Mangesh I., Nair, Jijeesh R., Pratt, Lawrence R., Soto, Fernando A., Balbuena, Perla B., and Rempe, Susan B. Fri . "Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion". United States. https://doi.org/10.1021/acs.jctc.6b00824. https://www.osti.gov/servlets/purl/1339276.
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@article{osti_1339276,
title = {Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion},
author = {Chaudhari, Mangesh I. and Nair, Jijeesh R. and Pratt, Lawrence R. and Soto, Fernando A. and Balbuena, Perla B. and Rempe, Susan B.},
abstractNote = {Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li+ to PC from water, based on electronic structure calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li+/PF6- transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial charges in simple, nonpolarizable force fields in future studies of these electrolyte solutions.},
doi = {10.1021/acs.jctc.6b00824},
journal = {Journal of Chemical Theory and Computation},
number = 12,
volume = 12,
place = {United States},
year = {Fri Oct 21 00:00:00 EDT 2016},
month = {Fri Oct 21 00:00:00 EDT 2016}
}
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