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Title: Density functional theory study of the capacitance of single file ions in a narrow cylinder

Abstract

In this paper, the differential capacitance of a model organic electrolyte in a cylindrical pore that is so narrow that the ions can form only a single file is studied by means of density functional theory (DFT). Kornyshev (2013), has studied this system and found the differential capacitance to have only a double hump shape (the so-called camel shape) whereas other geometries show this behavior only at low ionic concentrations that are typical for aqueous electrolytes. However, his calculation is rather approximate. In this DFT study we find that the double hump shape occurs only at low ionic concentrations. At high concentrations, the capacitance has only a single hump. Kornyshev considers a metallic cylinder and approximately includes the contributions of electrostatic images. Electrostatic images are not easily incorporated into DFT. In conclusion, images are not considered in this study and the question of whether Kornyshev’s result is due to his approximations or images cannot be answered. Simulations to answer this question are planned.

Authors:
 [1];  [1];  [2]
+ Show Author Affiliations
  1. Univ. of California, Riverside, CA (United States)
  2. Brigham Young Univ., Provo, UT (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1265472
Alternate Identifier(s):
OSTI ID: 1246727
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Colloid and Interface Science
Additional Journal Information:
Journal Volume: 449; Journal Issue: C; Journal ID: ISSN 0021-9797
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Single file nanopore; Cylindrical double layer; Capacitance; Density functional theory

Citation Formats

Kong, Xian, Wu, Jianzhong, and Henderson, Douglas. Density functional theory study of the capacitance of single file ions in a narrow cylinder. United States: N. p., 2014. Web. doi:10.1016/j.jcis.2014.11.012.
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Kong, Xian, Wu, Jianzhong, & Henderson, Douglas. Density functional theory study of the capacitance of single file ions in a narrow cylinder. United States. https://doi.org/10.1016/j.jcis.2014.11.012
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Kong, Xian, Wu, Jianzhong, and Henderson, Douglas. Fri . "Density functional theory study of the capacitance of single file ions in a narrow cylinder". United States. https://doi.org/10.1016/j.jcis.2014.11.012. https://www.osti.gov/servlets/purl/1265472.
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@article{osti_1265472,
title = {Density functional theory study of the capacitance of single file ions in a narrow cylinder},
author = {Kong, Xian and Wu, Jianzhong and Henderson, Douglas},
abstractNote = {In this paper, the differential capacitance of a model organic electrolyte in a cylindrical pore that is so narrow that the ions can form only a single file is studied by means of density functional theory (DFT). Kornyshev (2013), has studied this system and found the differential capacitance to have only a double hump shape (the so-called camel shape) whereas other geometries show this behavior only at low ionic concentrations that are typical for aqueous electrolytes. However, his calculation is rather approximate. In this DFT study we find that the double hump shape occurs only at low ionic concentrations. At high concentrations, the capacitance has only a single hump. Kornyshev considers a metallic cylinder and approximately includes the contributions of electrostatic images. Electrostatic images are not easily incorporated into DFT. In conclusion, images are not considered in this study and the question of whether Kornyshev’s result is due to his approximations or images cannot be answered. Simulations to answer this question are planned.},
doi = {10.1016/j.jcis.2014.11.012},
journal = {Journal of Colloid and Interface Science},
number = C,
volume = 449,
place = {United States},
year = {Fri Nov 14 00:00:00 EST 2014},
month = {Fri Nov 14 00:00:00 EST 2014}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1016/j.jcis.2014.11.012
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    Works referencing / citing this record:

    Lattice model of ionic liquid confined by metal electrodes
    journal, May 2018

    • Girotto, Matheus; Malossi, Rodrigo M.; dos Santos, Alexandre P.
    • The Journal of Chemical Physics, Vol. 148, Issue 19
    • DOI: 10.1063/1.5013337
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