A systematic Monte Carlo simulation study of the primitive model planar electrical double layer over an extended range of concentrations, electrode charges, cation diameters and valences
Source abstract
Abstract
The purpose of this study is to provide data for the primitive model of the planar electrical double layer, where ions are modeled as charged hard spheres, the solvent as an implicit dielectric background (with dielectric constant ϵ = 78.5), and the electrode as a smooth, uniformly charged, hard wall. We use canonical and grand canonical Monte Carlo simulations to compute the concentration profiles, from which the electric field and electrostatic potential profiles are obtained by solving Poisson’s equation. We report data for an extended range of parameters including 1:1, 2:1, and 3:1 electrolytes at concentrations c = 0.0001 − 1 M near electrodes carrying surface charges up to σ = ±0.5 Cm−2. The anions are monovalent with a fixed diameter d− = 3 Å, while the charge and diameter of cations are varied in the range z+ = 1, 2, 3 and d+ = 1.5, 3, 6, and 9 Å (the temperature is 298.15 K). We provide all the raw data in the supplementary material.
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Research context
OpenAlex topics: Electrostatics and Colloid Interactions · Geophysical and Geoelectrical Methods · Electrical and Bioimpedance Tomography
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Physical Chemistry, University of Pannonia 1 , P.O. Box 158, H-8201 Veszprém, Hungary
Department of Physiology and Biophysics, Rush University Medical Center 2 , Chicago, IL 60612, USA
Institute of Advanced Studies Kőszeg (iASK) 3 , Chernel st. 14., H-9730 Kőszeg, Hungary
Funding
GINOP · National Research, Development and Innovation Office · New National Excellence Program · National Science Foundation
References (81)
Show source-provided references
1. Sur la constitution de la charge electrique a la surface d’un electrolyte10.1051/jphystap:019100090045700 ↗
2. A contribution to the theory of electrocapillarity10.1080/14786440408634187 ↗
3. Zur theorie der elektrolytischen doppelschicht
4. Materials for electrochemical capacitors10.1038/nmat2297 ↗
5. Review on the science and technology of water desalination by capacitive deionization10.1016/j.pmatsci.2013.03.005 ↗
6. In situ, label-free DNA detection using organic transistor sensors10.1002/adma.201000790 ↗
7. Improving charge-sensitive biomolecule sensors with the right choice of electrolyte10.1016/j.snb.2016.02.057 ↗
8. Tailoring membrane nanostructure and charge density for high electrokinetic energy conversion efficiency10.1021/acsnano.5b07229 ↗
9. Electrokinetic energy conversion efficiency in nanofluidic channels10.1021/nl061524l ↗
10. Power generation by pressure-driven transport of ions in nanofluidic channels10.1021/nl070194h ↗
11. High energy conversion efficiency in nanofluidic channels10.1021/nl204087f ↗
12. XXXIX. Structure and capacity of electrical double layer10.1080/14786444208520813 ↗
13. Solution of Ornstein-Zernike equation for wall-particle distribution function10.1007/bf01020798 ↗
14. Theory of electrified interfaces10.1021/j100517a009 ↗
15. Application of the hypernetted chain approximation to the electric double-layer at a charged planar interface10.1016/0009-2614(79)87041-4 ↗
16. Theory of the electric double layer using a modified Poisson-Boltzman equation10.1039/f29807601388 ↗
17. Numerical solution of a modified Poisson-Boltzmann equation for 1:2 and 2:1 electrolytes in the diffuse layer10.1080/00268978100100961 ↗
18. The application of the hypernetted chain approximation to the electrical double-layer—Comparison with Monte-Carlo results for symmetric salts10.1063/1.443691 ↗
19. Application of the hypernetted chain approximation to the electrical double-layer—Comparison with Monte Carlo results for 2-1 and 1-2 salts10.1021/j100238a025 ↗
20. Pair correlation-functions and density profiles in the primitive model of the electric double-layer10.1063/1.454001 ↗
21. Free-energy model for the inhomogeneous hard-sphere fluid mixture and density-functional theory of freezing10.1103/physrevlett.63.980 ↗
22. Free-energy density functional for the inhomogeneous hard-sphere fluid—Application to interfacial adsorption10.1103/physreva.42.3382 ↗
23. A nonlocal free-energy density-functional approximation for the electrical double-layer10.1063/1.458542 ↗
24. Density-functional theory for inhomogeneous fluids—Adsorption of binary-mixtures10.1103/physreva.44.5025 ↗
25. Free-energy model for inhomogeneous fluid mixtures—Yukawa-charged hard-spheres, general interactions, and plasmas10.1063/1.464569 ↗
26. Fundamental-measure free-energy density functional for hard spheres: Dimensional crossover and freezing10.1103/physreve.55.4245 ↗
27. Liquid-vapor interface of an ionic fluid10.1103/physreve.57.6944 ↗
28. Monte Carlo, density functional theory, and Poisson-Boltzmann theory study of the structure of an electrolyte near an electrode10.1063/1.1464826 ↗
29. Coupling Poisson-Nernst-Planck and density functional theory to calculate ion flux10.1088/0953-8984/14/46/317 ↗
30. Density functional theory of charged, hard-sphere fluids10.1103/physreve.68.031503 ↗
31. Field theory for ionic systems. From fluctuations and structure at a hard wall to thermodynamics10.1016/s0013-4686(03)00362-1 ↗
32. Field theoretical approach to inhomogeneous ionic systems: thermodynamic consistency with the contact theorem, Gibbs adsorption and surface tension10.1080/0026897031000154293 ↗
33. Phase behavior of ionic fluids in slitlike pores: A density functional approach for the restricted primitive model10.1063/1.1818677 ↗
34. Density functional theory of the electrical double layer: The RFD functional10.1088/0953-8984/17/42/002 ↗
35. Temperature dependence of the double layer capacitance for the restricted primitive model of an electrolyte solution from a density functional approach10.1063/1.1850453 ↗
36. Selective adsorption of ions with different diameter and valence at highly-charged interfaces10.1021/jp073703c ↗
37. A self-consistent density-functional approach to the structure of electric double layer: Charge-asymmetric electrolytes10.1080/00268970802680497 ↗
38. Density functional study of the electric double layer formed by a high density electrolyte10.1021/jp2078105 ↗
39. Double layer in ionic liquids: Overscreening versus crowding10.1103/physrevlett.106.046102 ↗
40. The weighted correlation approach for density functional theory: A study on the structure of the electric double layer10.1088/0953-8984/23/17/175002 ↗
41. Electric double layer capacitance of restricted primitive model for an ionic fluid in slit-like nanopores: A density functional approach10.1063/1.4771919 ↗
42. Electrical double layers and differential capacitance in molten salts from density functional theory10.1063/1.4891368 ↗
43. Revisiting density functionals for the primitive model of electric double layers10.1063/1.4862990 ↗
44. A contact-corrected density functional theory for electrolytes at an interface10.1039/c3cp55130j ↗
45. Properties of a planar electric double layer under extreme conditions investigated by classical density functional theory and Monte Carlo simulations10.1063/1.4892415 ↗
46. Structure of a planar electric double layer containing size-asymmetric ions: Density functional approach10.1080/00268976.2014.985753 ↗
47. Influence of ion pairing in ionic liquids on electrical double layer structures and surface force using classical density functional approach10.1063/1.4919314 ↗
48. A systematic comparison of different approaches of density functional theory for the study of electrical double layers10.1063/1.4921376 ↗
49. Shells of charge: A density functional theory for charged hard spheres10.1088/0953-8984/28/24/244006 ↗
50. Electrical double-layers 4. Limitations of the Gouy-Chapman theory10.1021/j100213a035 ↗
51. Insights from theory and simulation on the electrical double layer10.1039/b815946g ↗
52. Monte-Carlo study of an electrical double-layer10.1016/0009-2614(79)87078-5 ↗
53. Electrical double-layers 1. Monte Carlo study of a uniformly charged surface10.1063/1.440065 ↗
54. The electrical double-layer 3. Modified Gouy-Chapman theory with unequal ion sizes10.1063/1.443542 ↗
55. Electrical double-layers 5. Asymmetric ion wall interactions10.1063/1.447535 ↗
56. The grand canonical ensemble Monte-Carlo method applied to the electrical double-layer10.1063/1.440657 ↗
57. Finite ion size effects in the electrical double-layer—A Monte-Carlo study10.1063/1.442571 ↗
58. (Almost) stationary isotachophoretic concentration boundary in a nanofluidic channel using charge inversion10.1021/acs.analchem.6b01701 ↗
59. A review of steric interactions of ions: Why some theories succeed and others fail to account for ion size10.1007/s10404-014-1489-5 ↗
60. Ion steric effects on electrophoresis of a colloidal particle10.1017/s0022112009991728 ↗
61. Some recent trends in computer simulations of aqueous double layers10.1016/j.electacta.2003.04.002 ↗
62. Mean spherical model integral equation for charged hard spheres I. Method of solution10.1063/1.1677644 ↗
63. Tuning transport properties of nanofluidic devices with local charge inversion10.1021/ja808717u ↗
64. Efficiently accounting for ion correlations in electrokinetic nanofluidic devices using density functional theory10.1016/j.jcis.2011.03.088 ↗
65. Ion correlations in nanofluidic channels: Effects of ion size, valence, and concentration on voltage- and pressure-driven currents10.1021/la304032t ↗
66. Monte Carlo study of the capacitance of the double layer in a model molten salt10.1063/1.478429 ↗
67. Low temperature anomalies in the properties of the electrochemical interface10.1016/s0009-2614(99)00643-0 ↗
68. A modified Poisson-Boltzmann analysis of the capacitance behavior of the electric double layer at low temperatures10.1063/1.1992427 ↗
69. Electrical double-layers 2. Monte-Carlo and HNC studies of image effects10.1063/1.443541 ↗
70. A modified Poisson-Boltzmann theory and Monte Carlo simulation study of surface polarization effects in the planar diffuse double layer10.1080/00268970701355795 ↗
71. The behavior of 2:1 and 3:1 electrolytes at polarizable interfaces10.1021/je101141a ↗
72. On the interfacial capacitance of an electrolyte at a metallic electrode around zero surface charge10.1080/00268976.2012.745954 ↗
73. A comparative study of room temperature ionic liquids and their organic solvent mixtures near charged electrodes10.1088/0953-8984/28/46/464002 ↗
74. Monte Carlo study of molten salt with charge asymmetry near the electrode surface10.1063/1.4862998 ↗
75. Influence of temperature on the capacitance of ionic liquid electrolytes on charged surfaces10.1039/c3cp54705a ↗
76. Size asymmetric hard spheres as a convenient model for the capacitance of the electrical double layer of an ionic liquid
77. Monte Carlo simulation of an ion-dipole mixture as a model of an electrical double layer10.1063/1.477342 ↗
78. Simulating prescribed particle densities in the grand canonical ensemble using iterative algorithms10.1063/1.2839302 ↗
79. An efficient iterative grand canonical Monte Carlo algorithm to determine individual ionic chemical potentials in electrolytes10.1063/1.3443558 ↗
80. Calculating the electrostatic potential profiles of double layers from simulation ion density profiles
81. 2009