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Spatial resolution of the electrical conductance of ionic fluids using a Green-Kubo method

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4901035· OSTI ID:1502449
 [1];  [2];  [3]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Mechanics of Materials Dept.
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Materials Chemistry Dept.
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Thermal/Fluid Science and Engineering Dept.
+ Show Author Affiliations

We present a Green-Kubo method to spatially resolve transport coefficients in compositionally heterogeneous mixtures. We develop the underlying theory based on well-known results from mixture theory, Irving-Kirkwood field estimation, and linear response theory. Then, using standard molecular dynamics techniques, we apply the methodology to representative systems. With a homogeneous salt water system, where the expectation of the distribution of conductivity is clear, we demonstrate the sensitivities of the method to system size, and other physical and algorithmic parameters. Then we present a simple model of an electrochemical double layer where we explore the resolution limit of the method. In this system, we observe significant anisotropy in the wall-normal vs. transverse ionic conductances, as well as near wall effects. Lastly, we discuss extensions and applications to more realistic systems such as batteries where detailed understanding of the transport properties in the vicinity of the electrodes is of technological importance.

Research Organization:
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1502449
Report Number(s):
SAND--2014-15846J; 672036
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 141; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Local viscoelasticity at resin-metal interface analyzed with spatial-decomposition formula for relaxation modulus journal September 2019
Method to manage integration error in the Green-Kubo method journal February 2017

Figures / Tables (13)

FIG. 1(p. 3)figure FIG. 1
FIG. 2(p. 13)figure FIG. 2
TABLE I(p. 16)table TABLE I
FIG. 3(p. 17)figure FIG. 3
FIG. 4(p. 19)figure FIG. 4
FIG. 5(p. 20)figure FIG. 5
FIG. 6(p. 20)figure FIG. 6
FIG. 7(p. 23)figure FIG. 7
FIG. 8(p. 23)figure FIG. 8
FIG. 10(p. 24)figure FIG. 10
FIG. 9(p. 24)figure FIG. 9
FIG. 11(p. 25)figure FIG. 11
FIG. 12(p. 25)figure FIG. 12

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY