Li+ solvation and kinetics of Li+–BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories
Abstract
Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine in this paper the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+–[BF4] and Li+–[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li+ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li+–[BF4] to Li+–[PF6] ion pairs in EC. Finally, our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.
- Authors:
-
- Univ. of Wisconsin-Parkside, Kenosha, WI (United States). Dept. of Chemistry
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1430712
- Alternate Identifier(s):
- OSTI ID: 1371791
- Report Number(s):
- PNNL-SA-125713
Journal ID: ISSN 0021-9606; TRN: US1802920
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 147; Journal Issue: 16; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; disperse systems; condensed matter properties; optical metrology; optical properties; thermodynamic properties; computational methods; solvents; chemical solutions; computer simulation; optical constants
Citation Formats
Chang, Tsun-Mei, and Dang, Liem X. Li+ solvation and kinetics of Li+–BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories. United States: N. p., 2017.
Web. doi:10.1063/1.4991565.
Chang, Tsun-Mei, & Dang, Liem X. Li+ solvation and kinetics of Li+–BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories. United States. https://doi.org/10.1063/1.4991565
Chang, Tsun-Mei, and Dang, Liem X. Wed .
"Li+ solvation and kinetics of Li+–BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories". United States. https://doi.org/10.1063/1.4991565. https://www.osti.gov/servlets/purl/1430712.
@article{osti_1430712,
title = {Li+ solvation and kinetics of Li+–BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories},
author = {Chang, Tsun-Mei and Dang, Liem X.},
abstractNote = {Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine in this paper the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+–[BF4] and Li+–[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li+ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li+–[BF4] to Li+–[PF6] ion pairs in EC. Finally, our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.},
doi = {10.1063/1.4991565},
journal = {Journal of Chemical Physics},
number = 16,
volume = 147,
place = {United States},
year = {Wed Jul 19 00:00:00 EDT 2017},
month = {Wed Jul 19 00:00:00 EDT 2017}
}
Web of Science
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Works referencing / citing this record:
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