Charge oscillations in ionic liquids: A microscopic cluster model

被引:42
作者
Avni, Yael [1 ,2 ]
Adar, Ram M. [1 ,2 ]
Andelman, David [1 ,2 ]
机构
[1] Raymond & Beverly Sackler Sch Phys & Astron, IL-69978 Tel Aviv, Israel
[2] Tel Aviv Univ, IL-69978 Tel Aviv, Israel
基金
以色列科学基金会;
关键词
POISSON-BOLTZMANN; DOUBLE-LAYER; ELECTROLYTES; CAPACITANCE; FORCES; LENGTH; FLUID;
D O I
10.1103/PhysRevE.101.010601
中图分类号
O35 [流体力学]; O53 [等离子体物理学];
学科分类号
070204 ; 080103 ; 080704 ;
摘要
In spite of their enormous applications as alternative energy storage devices and lubricants, room-temperature ionic liquids (ILs) still pose many challenges from a pure scientific viewpoint. We develop an IL microscopic theory in terms of ionic clusters, which describes the IL behavior close to charged interfaces. The full structure factor of finite-size clusters is considered and allows us to retain fine and essential details of the system as a whole. Beside the reduction in the screening, it is shown that ionic clusters cause the charge density to oscillate near charged boundaries, with alternating ion-size thick layers, in agreement with experiments. We distinguish between short-range oscillations that persist for a few ionic layers close to the boundary, as opposed to long-range damped oscillations that hold throughout the bulk. The former can be captured by finite-size ion pairs, while the latter is associated with larger clusters with a pronounced quadrupole (or higher) moment. The long-wavelength limit of our theory recovers the well-known Bazant-Storey-Kornyshev (BSK) equation in the linear regime, and elucidates the microscopic origin of the BSK phenomenological parameters.
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页数:6
相关论文
共 59 条
  • [1] THE INFLUENCE OF CONCENTRATION AND IONIC-STRENGTH ON THE CLUSTER STRUCTURE OF HIGHLY-CHARGED ELECTROLYTE-SOLUTIONS
    ABASCAL, JLF
    BRESME, F
    TURQ, P
    [J]. MOLECULAR PHYSICS, 1994, 81 (01) : 143 - 156
  • [2] Screening length for finite-size ions in concentrated electrolytes
    Adar, Ram M.
    Safran, Samuel A.
    Diamant, Haim
    Andelman, David
    [J]. PHYSICAL REVIEW E, 2019, 100 (04):
  • [3] Bjerrum pairs in ionic solutions: A Poisson-Boltzmann approach
    Adar, Ram M.
    Markovich, Tomer
    Andelman, David
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2017, 146 (19)
  • [4] Armand M., 2011, MAT SUSTAINABLE ENER, P129, DOI DOI 10.1142/9789814317665_0020
  • [5] Double Layer in Ionic Liquids: Overscreening versus Crowding
    Bazant, Martin Z.
    Storey, Brian D.
    Kornyshev, Alexei A.
    [J]. PHYSICAL REVIEW LETTERS, 2011, 106 (04)
  • [6] Bjerrum N., 1926, KGL DANSKE VIDENSKAB, V7, P1
  • [7] Structural interactions in ionic liquids linked to higher-order Poisson-Boltzmann equations
    Blossey, R.
    Maggs, A. C.
    Podgornik, R.
    [J]. PHYSICAL REVIEW E, 2017, 95 (06)
  • [8] Static nonlocal dielectric function of liquid water
    Bopp, PA
    Kornyshev, AA
    Sutmann, G
    [J]. PHYSICAL REVIEW LETTERS, 1996, 76 (08) : 1280 - 1283
  • [9] Steric effects in electrolytes: A modified Poisson-Boltzmann equation
    Borukhov, I
    Andelman, D
    Orland, H
    [J]. PHYSICAL REVIEW LETTERS, 1997, 79 (03) : 435 - 438
  • [10] Nonlocal statistical field theory of dipolar particles in electrolyte solutions
    Budkov, Yury A.
    [J]. JOURNAL OF PHYSICS-CONDENSED MATTER, 2018, 30 (34)