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Title: Li + solvation and kinetics of Li +–BF 4 -/PF 6 - 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 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 the residence times of EC around Li+ ions varied from 70 to 450 ps, depending on the correction method used. We found the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influence the dissociation kinetics of ion pairing. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.

Authors:
ORCiD logo [1];  [2]
  1. Department of Chemistry, University of Wisconsin–Parkside, Kenosha, Wisconsin 53141, USA
  2. Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 93352, USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1422313
Report Number(s):
PNNL-SA-125713
Journal ID: ISSN 0021-9606; KC0301050
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 147; Journal Issue: 16
Country of Publication:
United States
Language:
English

Citation Formats

Chang, Tsun-Mei, and Dang, Liem X. Li + solvation and kinetics of Li+–BF4-/PF 6 - 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-/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories. United States. doi:10.1063/1.4991565.
Chang, Tsun-Mei, and Dang, Liem X. Sat . "Li + solvation and kinetics of Li+–BF4-/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories". United States. doi:10.1063/1.4991565.
@article{osti_1422313,
title = {Li + solvation and kinetics of Li+–BF4-/PF 6 - 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 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 the residence times of EC around Li+ ions varied from 70 to 450 ps, depending on the correction method used. We found the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influence the dissociation kinetics of ion pairing. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.},
doi = {10.1063/1.4991565},
journal = {Journal of Chemical Physics},
number = 16,
volume = 147,
place = {United States},
year = {Sat Oct 28 00:00:00 EDT 2017},
month = {Sat Oct 28 00:00:00 EDT 2017}
}