Giant charge reversal has been identified for the first time by Monte Carlo simulation for a discretely charged surface in contact with a trivalent electrolyte solution. It takes place regardless of the surface charge density under study and the monovalent salt. In stark contrast to earlier predictions based on the 2-dimensional Wigner crystal model to describe strong correlation of counterions at the macroion surface, we find that giant charge reversal reflects an intricate interplay of ionic volume effects, electrostatic correlations, surface charge heterogeneity, and the dielectric response of the confined fluids. While the novel phenomenon is yet to be confirmed with experiment, the simulation results appear in excellent agreement with a wide range of existing observations in the subregime of charge inversion. Our findings may have far-reaching implications to understanding complex electrochemical phenomena entailing ionic fluids under dielectric confinements.
REFERENCES
1.
A. Y.
Grosberg
, T. T.
Nguyen
, and B. I.
Shklovskii
, “Colloquium: The physics of charge inversion in chemical and biological systems
,” Rev. Mod. Phys.
74
, 329
(2002
).2.
J.
Lyklema
, “Overcharging, charge reversal: Chemistry or physics?
,” Colloids Surf., A
291
, 3
(2006
).3.
M. G.
Bungenberg de Jong
, in Colloid Science
, edited by H. R.
Kruyt
(Elsevier
, New York
, 1949
), p. 335
.4.
U. P.
Strauss
, N. L.
Gershfeld
, and H.
Spiera
, “Charge reversal of cationic poly-4-vinylpyridine derivatives in KBr solutions
,” J. Am. Chem. Soc.
76
, 5909
(1954
).5.
T. T.
Nguyen
, A. Y.
Grosberg
, and B. I.
Shklovskii
, “Macroions in salty water with multivalent ions: Giant inversion of charge
,” Phys. Rev. Lett.
85
, 1568
(2000
).6.
T. T.
Nguyen
, A. Y.
Grosberg
, and B. I.
Shklovskii
, “Screening of a charged particle by multivalent counterions in salty water: Strong charge inversion
,” J. Chem. Phys.
113
, 1110
(2000
).7.
M.
Miller
, M.
Chu
, B.
Lin
, M.
Meron
, and P.
Dutta
, “Observation of ordered structures in counterion layers near wet charged surfaces: A potential mechanism for charge inversion
,” Langmuir
32
, 73
(2016
).8.
S.
Pianegonda
, M. C.
Barbosa
, and Y.
Levin
, “Charge reversal of colloidal particles
,” Europhys. Lett.
71
, 831
(2005
).9.
O.
Lenz
and C.
Holm
, “Simulation of charge reversal in salty environments: Giant overcharging?
,” Eur. Phys. J. E
26
, 191
(2008
).10.
S. S.
Lee
, M.
Schmidt
, N.
Laanait
, N. C.
Sturchio
, and P.
Fenter
, “Investigation of structure, adsorption free energy, and overcharging behavior of trivalent yttrium adsorbed at the muscovite (001)-water interface
,” J. Phys. Chem. C
117
, 23738
(2013
).11.
A.
Diehl
and Y.
Levin
, “Smoluchowski equation and the colloidal charge reversal
,” J. Chem. Phys.
125
, 054902
(2006
).12.
M.
Quesada-Pérez
, A.
Martín-Molina
, and R.
Hidalgo-Álvarez
, “Simulation of electric double layers undergoing charge inversion: Mixtures of mono- and multivalent ions
,” Langmuir
21
, 9231
(2005
).13.
Y.
Chen
, Z.
Ni
, G.
Wang
, D.
Xu
, and D.
Li
, “Electroosmotic flow in nanotubes with high surface charge densities
,” Nano Lett.
8
, 42
(2008
).14.
Z.-Y.
Wang
and Y.-Q.
Ma
, “Insights from Monte Carlo simulations on charge inversion of planar electric double layers in mixtures of asymmetric electrolytes
,” J. Chem. Phys.
133
, 064704
(2010
).15.
A.
Martín-Molina
, M.
Quesada-Pérez
, F.
Galisteo-González
, and R.
Hidalgo-Álvarez
, “Probing charge inversion in model colloids: Electrolyte mixtures of multi- and monovalent counterions
,” J. Phys.: Condens. Matter
15
, S3475
(2003
).16.
F. H. J.
van der Heyden
, D.
Stein
, K.
Besteman
, S. G.
Lemay
, and C.
Dekker
, “Charge inversion at high ionic strength studied by streaming currents
,” Phys. Rev. Lett.
96
, 224502
(2006
).17.
A.
Martín-Molina
, C.
Rodríguez-Beas
, and J.
Faraudo
, “Charge reversal in anionic liposomes: Experimental demonstration and molecular origin
,” Phys. Rev. Lett.
104
, 168103
(2010
).18.
A. G.
Moreira
and R. R.
Netz
, “Counterions at charge-modulated substrates
,” Europhys. Lett.
57
, 911
(2002
).19.
S.
Taheri-Araghi
and B.-Y.
Ha
, “Charge renormalization and inversion of a highly charged lipid bilayer: Effects of dielectric discontinuities and charge correlations
,” Phys. Rev. E
72
, 021508
(2005
).20.
Z.-Y.
Wang
and Y.-Q.
Ma
, “Impact of head group charges, ionic sizes, and dielectric images on charge inversion: A Monte Carlo simulation study
,” J. Phys. Chem. B
114
, 13386
(2010
).21.
Z.
Gan
and Z.
Xu
, “Multiple-image treatment of induced charges in Monte Carlo simulations of electrolytes near a spherical dielectric interface
,” Phys. Rev. E
84
, 016705
(2011
).22.
A.
Naji
, M.
Ghodrat
, H.
Komaie-Moghaddam
, and R.
Podgornik
, “Asymmetric Coulomb fluids at randomly charged dielectric interfaces: Anti-fragility, overcharging and charge inversion
,” J. Chem. Phys.
141
, 174704
(2014
).23.
Z.-Y.
Wang
, “Charge reversal at a planar boundary between two dielectrics
,” Phys. Rev. E
93
, 012605
(2016
).24.
Z.-Y.
Wang
and Z.
Ma
, “Examining the contributions of image-charge forces to charge reversal: Discrete versus continuum modeling of surface charges
,” J. Chem. Theory Comput.
12
, 2880
(2016
).25.
M. Y.
Kiriukhin
and K. D.
Collins
, “Dynamic hydration numbers for biologically important ions
,” Biophys. Chem.
99
, 155
(2002
).26.
J.
Sala
, E.
Guàrdia
, and J.
Martí
, “Specific ion effects in aqueous eletrolyte solutions confined within graphene sheets at the nanometric scale
,” Phys. Chem. Chem. Phys.
14
, 10799
(2012
).27.
K.
Besteman
, M. A. G.
Zevenbergen
, and S. G.
Lemay
, “Charge inversion by multivalent ions: Dependence on dielectric constant and surface-charge density
,” Phys. Rev. E
72
, 061501
(2005
).28.
G.
Cevc
, “Membrane electrostatics
,” Biochim. Biophys. Acta
1031
, 311
(1990
).29.
W. F.
Heinz
and J. H.
Hoh
, “Relative surface charge density mapping with the atomic force microscope
,” Biophys. J.
76
, 528
(1999
).30.
M. P.
Allen
and D. J.
Tildesley
, Computer Simulation of Liquids
(Oxford University Press
, Oxford
, 1987
).31.
A.
Grzybowski
and A.
Bródka
, “Coulomb interactions in a computer simulation of a system periodic in two directions
,” Mol. Phys.
100
, 1017
(2002
).32.
Y.
Wang
, R.
Wang
, B.
Cao
, Z.
Guo
, and G.
Yang
, “Single molecular demonstration of modulating charge inversion of DNA
,” Sci. Rep.
6
, 38628
(2016
).33.
S.
Madurga
, A.
Martín-Molina
, E.
Vilaseca
, F.
Mas
, and M.
Quesada-Pérez
, “Effect of the surface charge discretization on electric double layers: A Monte Carlo simulation study
,” J. Chem. Phys.
126
, 234703
(2007
).34.
C.
Calero
and J.
Faraudo
, “The interaction between electrolyte and surfaces decorated with charged groups: A molecular dynamics simulation study
,” J. Chem. Phys.
132
, 024704
(2010
).35.
S.
Vangaveti
and A.
Travesset
, “General solution to the electric double layer with discrete interfacial charges
,” J. Chem. Phys.
137
, 064708
(2012
).36.
M. M.
Hatlo
and L.
Lue
, “The role of image charges in the interactions between colloidal particles
,” Soft Matter
4
, 1582
(2008
).37.
A.
Bakhshandeh
, A. P.
dos Santos
, and Y.
Levin
, “Weak and strong coupling theories for polarizable colloids and nanoparticles
,” Phys. Rev. Lett.
107
, 107801
(2011
).38.
V.
Jadhao
, F. J.
Solis
, and M.
Olvera de la Cruz
, “Simulation of charged systems in heterogeneous dielectric media via a true energy functional
,” Phys. Rev. Lett.
109
, 223905
(2012
).39.
A.
Travesset
and D.
Vaknin
, “Bjerrum pairing correlations at charged interfaces
,” Europhys. Lett.
74
, 181
(2006
).40.
J.
Pittler
, W.
Bu
, D.
Vaknin
, A.
Travesset
, D. J.
McGillivray
, and M.
Lösche
, “Charge inversion at minute electrolyte concentrations
,” Phys. Rev. Lett.
97
, 046102
(2006
).41.
M.
Aguilella-Arzo
, A.
Andrio
, V. M.
Aguilella
, and A.
Alcaraz
, “Dielectric saturation of water in a membrane protein channel
,” Phys. Chem. Chem. Phys.
11
, 358
(2009
).42.
K.
Morikawa
, Y.
Kazoe
, K.
Mawatari
, T.
Tsukahara
, and T.
Kitamori
, “Dielectric constant of liquids confined in the extended nanospace measured by a streaming potential method
,” Anal. Chem.
87
, 1475
(2015
).43.
E.
Wernersson
, R.
Kjellander
, and J.
Lyklema
, “Charge inversion and ion-ion correlation effects at the mercury/aqueous MgSO4 interface: Toward the solution of a long-standing issue
,” J. Phys. Chem. C
114
, 1849
(2010
).© 2017 Author(s).
2017
Author(s)
You do not currently have access to this content.