Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion [electronic resource].
- Washington, D.C. : United States. Office of the Assistant Secretary of Energy Efficiency and Renewable Energy, 2016.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
- Physical Description:
- pages 5,709-5,718 : digital, PDF file
- Additional Creators:
- Sandia National Laboratories
United States. Office of the Assistant Secretary of Energy Efficiency and Renewable Energy
United States. Department of Energy. Office of Scientific and Technical Information
- 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<sup>+</sup> 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<sup>+</sup>/PF<sub>6</sub><sup>-</sup> 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.
- Published through SciTech Connect.
Journal of Chemical Theory and Computation 12 12 ISSN 1549-9618 AM
Mangesh I. Chaudhari; Jijeesh R. Nair; Lawrence R. Pratt; Fernando A. Soto; Perla B. Balbuena; Susan B. Rempe.
- Funding Information:
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