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Hybrid DFT Functional-Based Static and Molecular Dynamics Studies of Excess Electron in Liquid Ethylene Carbonate

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/1.3545977· OSTI ID:1064939
 [1];  [1];  [2];  [3]
  1. Texas A & M Univ., College Station, TX (United States)
  2. Frostburg State Univ., MD (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

We applied static and dynamic hybrid functional density functional theory (DFT) calculations to study the interactions of one and two excess electrons with ethylene carbonate (EC) liquid and clusters. Optimal structures of (EC)n and (EC)n- clusters devoid of Li+ ions, n = 1–6, were obtained. The excess electron was found to be localized on a single EC in all cases, and the EC dimeric radical anion exhibits a reduced barrier associated with the breaking of the ethylene carbon–oxygen covalent bond compared to EC-. In ab initio molecular dynamics (AIMD) simulations of EC- solvated in liquid EC, large fluctuations in the carbonyl carbon–oxygen bond lengths were observed. AIMD simulations of a two-electron attack on EC in EC liquid and on Li metal surfaces yielded products similar to those predicted using nonhybrid DFT functionals, except that CO release did not occur for all attempted initial configurations in the liquid state.

Research Organization:
Energy Frontier Research Centers (EFRC), Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Organization:
USDOE SC Office of Basic Energy Sciences (SC-22)
DOE Contract Number:
SC0001160
OSTI ID:
1064939
Journal Information:
Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 4 Vol. 158; ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English

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