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Charge Reversal of Surfaces in Divalent Electrolytes:

The Role of Ionic Dispersion Interactions
Drew F. Parsons* and Barry W. Ninham
Research School of Physical Sciences and Engineering, Australian National University,
Canberra, ACT 0200, Australia

Received October 30, 2009. Revised Manuscript Received January 7, 2010

Surface potentials of alkali earth nitrates at a mica surface are calculated using a modified Poisson-Boltzmann
approach that includes nonelectrostatic ion-surface dispersion interactions. New ab initio dynamic polarizabilities are
used to determine dispersion interactions. A hydration model describing the hydration shell of cations is presented.
Excellent agreement with experiment is achieved, including charge reversal at high electrolyte concentration without the
need for site binding models. This suggests that specific ionic dispersion forces provide the mechanism for ion surface
binding. An asymptotic surface potential is found in the limit of very high concentration. A Hofmeister series is
predicted according to the strength of charge reversal, with Mg > Ca > Sr > Ba. The ion-surface dispersion
adsorption energies of hydrated ions appear to explain the apparent repulsive secondary hydration forces observed
experimentally between mica surfaces when taken with a surface hydration layer.

Introduction especially when complications due to surfactants are involved.8

The measurement of a surface potential provides the standard
characterization of the surface properties of colloids. The inter-
pretation of surface potentials via double layer theory allows the
relationship between surface charge and surface potential to be
determined directly. Usually, the connection is made by the
electrostatic Poisson-Boltzmann model. The relationship is
“direct” in the sense that if the surface charge is positive then
the surface potential is positive. Conversely, if the surface charge
is negative then the surface potential is negative. Screening by an
electrolyte at higher concentrations implies that that the magni-
tude of the surface potential is reduced. In a simple electrostatic
theory, counterions will be attracted to the surface, effectively
neutralizing the surface charge so that the overall electrostatic
potential decreases. However, the counterion charge at the sur-
face may never exceed the original bare surface charge. It can do
no more than neutralize it. As the electrolyte concentration
increases, the magnitude of the surface potential will reduce
asymptotically to zero with a purely electrostatic interpretation.
In the absence of additional effects such as chemisorption or
physisorption of ions to the surface, or ion-ion spatial correla-
tions,1,2 the surface potential may never cross zero. Physisorption
via ion-surface dispersion interactions is addressed in this paper,
while ion-ion correlations are not.
In real systems, reversal of the surface polarity is indeed found.
Charge reversal is obtained trivially by varying pH in biological
systems due to protonation of acidic carboxylate and basic amine
groups.3,4 At mineral surfaces, charge reversal is more subtle. pH
charge reversal effects may appear depending on the mineral,5-7
*To whom correspondence should be addressed.
(1) Greberg, H.; Kjellander, R. J. Chem. Phys. 1998, 108, 2940–2953.


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Surf., B 2001, 21, 125–135.
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Mesoporous Mater. 2009, 122, 99–104.
But more interesting is the appearance of charge reversal as a
function of electrolyte concentration alone. In contradiction to
simple electrostatic theory, at sufficiently high concentration,
some electrolytes can induce a reversal in the surface polarity.
This can occur in 1:1 electrolytes,9-11 but it is more commonly
observed with multivalent ions, both cations8,12,13 and anions.7
This kind of charge reversal has been interpreted theoretically
by invoking site binding models.14-18 In these models, in an
extension of the original charge regulation model,19 the intrinsic
surface charge σ0 is modified by a surface layer of adsorbed
(“bound”) counterion σc. The amount of σc is established by a
postulated equilibrium between the bulk counterion C in solution
and SC, bound to a surface site S,
S þ C h SC ð1Þ
The equilibrium constant Kc for this system is determined by a
fitted surface binding energy. The counterion surface charge σc
is then obtained from the adsorbed ion concentration [SC].
The total surface charge, σ = σ0 þ σc, may change polarity if
|σc| > |σ0|. Essentially, the site binding model enables a larger
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6430 DOI: 10.1021/la9041265 Published on Web 01/29/2010 Langmuir 2010, 26(9), 6430–6436
Parsons and Ninham
concentration of counterion to be found at the surface than would
be the case due to simple electrostatic interactions alone. This
results in charge reversal rather than charge neutralization. The
success of the site binding model hinges on the reality of the
surface equilibrium constant Kc. In some cases, it is simply treated
as a fitting parameter to match experiment.16,17 In other works, it
is simply identified with the counterion concentration at the
surface.15
The role of nonelectrostatic ionic forces, that is, quantum
mechanically based van der Waals or dispersion forces, in
explaining ion specific effects has become apparent over the past
decade or so.20 These ion specific forces are ignored in classical
electrostatic theory, whether or not the theory is extended to
include “hydration”. Their inclusion goes some way toward
explaining deviations from pure electrostatic theory both in bulk
solution, for example, self-energies and activity coefficients,21-23
and at surfaces, for example, ion specific direct force measure-
ments.24-29 Ion specificity (Hofmeister effects) in this theory
occur due to dispersion forces. The specificity arises due to the
different dynamic polarizabilities R(iω) of the ions that determine
their interactions. At the same time, the importance of ionic and
molecular polarizabilities has also become clear in molecular
dynamics simulations. Polarizable water models such as q-
TIP4P/F30 or TIP4P-FQ31,32 reproduce bulk properties such as
water dipole, temperature-dependent density, and dielectric con-
stant. Likewise, polarizable potential models for ions show a
tremendous influence on the surface affinities of ions at an
interface predicted by computer simulation,32-34 with ionic
polarizability enabling positive adsorption of ions to the air-
water interface.
In this paper, we explore how ion-surface dispersion forces
may explain the phenomenon of surface charge reversal (or more
precisely, reversal in the polarity of the surface potential). The
nonelectrostatic dispersion potentials appear naturally alongside
electrostatic interactions in a modified Poisson-Boltzmann de-
scription of the electrolyte. We obtain charge reversal without
having to invoke a site binding model of unknown origin. We
therefore argue that dispersion forces provide the underlying
mechanism by which the “site binding model” operates. A
correspondence may be established between our theory and the
site binding model by identifying the ion dispersion interaction at
the surface with the surface binding energy, rather than treating it
as a fitting parameter. The surface binding model may be thought
of as a special case of the general theory of nonelectrostatic
interactions which considers nonelectrostatic interactions at the
interface alone. The general theory also includes nonelectrostatic
ionic forces in the bulk solution away from the surface.
(20) Ninham, B.; Yaminsky, V. Langmuir 1997, 13, 2097–2108.
(21) Parsons, D. F.; Deniz, V.; Ninham, B. W. Colloids Surf., A 2009, 343, 57–63.
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D. J. Curr. Opin. Colloid Interface Sci. 2004, 9, 67–73.
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Langmuir 2010, 26(9), 6430–6436
Article
In previous papers, the dynamic polarizabilities underpinning a
theory that includes dispersion forces have applied a single mode
model of the polarizabilities. The modal frequencies were inferred
from ionization potentials. Compared to ab initio polarizabilities,
the single mode model badly underestimates polarizabilities,
especially for halide anions and at the optical/UV frequencies
relevant to dispersion forces.10,21 We have recently reported
ab initio polarizabilities for monovalent monatomic ions.35 We
here report the ab initio polarizabilities for multivalent mona-
tomic cations and for the polyatomic water molecule and nitrate
anion. Water and nitrate are in reality nonspherical; however, for
simplicity, we apply a mean spherical approximation to them.
Theoretical Model
The surface potential may be estimated in a Poisson-
Boltzmann approach by calculating the electrostatic potential
ψ(z) due to the combination of surface charge and electrolyte
charge in solution. The surface potential is the value of ψ at z = 0.
ψ(z) is obtained by solving the Poisson equation
d2 ψ X
ε0 ε 2
¼ - qi ci ðzÞ ð2Þ
dz
i
where ci(z) is the concentration profile of ion i and qi is its charge. ε
is the dielectric constant of the solvent (water, ε = 78.36), and ε0 is
the permittivity of a vacuum. We have assumed a planar surface
here. The boundary condition for the Poisson equation is related
to the surface charge. We adopt a boundary condition of constant
surface charge σ0 at z = 0,
dψ σ0
¼ - ð3Þ
dz ε0 ε
Surface charge will vary with pH due to protonation of surface
charge sites. By adopting constant surface charge, we imply that
our calculations are conducted at fixed pH. The magnitude of our
surface charge is calibrated against experimental surface poten-
tials measured15 at pH 5.9. The fitted surface charge is taken to lie
at z = 0, and ions are permitted to occupy the volume where z g 0,
right up to the surface. Some implications of finite size effects,
with the ion radius providing a distance of closest approach to the
surface, are discussed at the end of this paper.
Ion concentrations are given as Boltzmann factors determined
by the free energy of the ion,
ci ðzÞ ¼ ci0 exp½ - Fi ðzÞ=kT ð4Þ
ci0 is the bulk concentration of ion i. We take the free energy to be
the sum of the electrostatic interaction energy qiψ of the ion inside
the electrostatic potential, plus the nonelectrostatic ion-surface
dispersion interactions Ui. That is,
Fi ðzÞ ¼ qi ψðzÞ þ Ui ðzÞ ð5Þ
The conventional application of the Poisson-Boltzmann
model at a surface, as used here, does not include ion-ion
interactions. These could be modeled within the same PB frame-
work by adding an additional term to eq 5, which would integrate
the interactions of ion i with other ions j in the volume between
surfaces.36 Alternatively ion-ion interactions and ion-ion
(35) Parsons, D. F.; Ninham, B. W. Langmuir 2010, 26, 1816-1823.
(36) Burak, Y.; Andelman, D. J. Chem. Phys. 2001, 114, 3271–3283.
DOI: 10.1021/la9041265 6431
Article
correlations (including finite ion size effects) could be included via
integral equation methods such the hypernetted chain (HNC)
model.37,38 Ion-ion correlation effects become particularly sig-
nificant at very high concentrations, but at the same considerably
increase the computational cost of the calculation. At the same
time, ion-surface dispersion interactions, which we do include
via Ui, should be more significant than ion-ion dispersion
interactions, since the former decay with 1/z3 (see eq 6 below)
while the latter decay more quickly,21 with 1/r6. Hence, while a
superior model would be constructed by including ion-ion size
correlations, any discrepancy due to the neglect of ion-ion
dispersion interactions should be relatively mild.
In classical electrostatic Derjaguin-Landau-Verwey-
Overbeek (DLVO) theory, Ui = 0; that is, ionic dispersion forces
are neglected. In fact, the classical DLVO theory, that handles
electrostatic forces in a nonlinear theory and electrodynamic
fluctuation (dispersion) forces not at all or separately in a linear
theory, can be proven to be physically inconsistent.20 However,
ionic dispersion forces lie at the heart of our model, they are
treated nonlinearly via eq 4, and they enable charge reversal to
occur.
Ion-Surface Dispersion Interactions. Ionic dispersion in-
teractions are driven by the dynamic polarizability Ri(iω) of an
ion, with the bulk of the interaction coming from the polariz-
ability at optical/UV frequencies. We adopt a semiclassical model
of polarizability which includes finite ion size.10,35,39 The ion
polarizability is taken to be spatially spread, following the ion’s
electron density, in a spherical Gaussian cloud exp(-r2/ai2)with
Gaussian radius ai. The resulting ion-surface dispersion interac-
tion is given by35,39-42
Bi hi ðzÞ
Ui ðzÞ ¼
z3
where
" # ! " #  
2z 2z2 z2 4z4 z R0 is the static polarizability, and fj and ωj are the weight and
hi ðzÞ ¼ 1 þ pffiffiffi - 1 exp - - 1 þ erfc
πai ai 2 ai 2 ai 4 ai
The surface dispersion coefficient Bi is calculated from the excess
dynamic polarizability Ri*(iω) of the ion, multiplied by the
difference in the dielectric responses of surface and solvent and
summed over imaginary frequencies iωn, where ωn = 2πnkT/p:
 the single mode ionization potential model is particularly stark,
kT X0 Ri ðiωn Þ Δðiωn Þ
B ¼
2 n εw ðiωn Þ
with
εw ðiωÞ - εs ðiωÞ
ΔðiωÞ ¼
εw ðiωÞ þ εs ðiωÞ
The prime (0 ) next to the summation symbol (Σ0 ) in eq 8 means
that the n = 0 term is taken with a factor 1/2. εw(iω) and εs(iω) are
the dielectric functions of solvent (water) and surface, respec-
tively. We use the water dielectric susceptibility function deter-
(37) Kjellander, R. J. Chem. Phys. 1988, 88, 7129–7137.
(38) Wernersson, E.; Kjellander, R. J. Phys. Chem. B 2007, 111, 14279–14284.
(39) Mahanty, J.; Ninham, B. W. Faraday Discuss. Chem. Soc. 1975, 59, 13–21.
(40) Mahanty, J.; Ninham, B. W. Dispersion Forces; Academic Press: London,
1976.
(41) Mahanty, J.; Ninham, B. W. J. Chem. Phys. 1973, 59, 6157–6162.
(42) Mahanty, J.; Ninham, B. J. Chem. Soc., Faraday Trans. 2 1974, 70, 637–650.
6432 DOI: 10.1021/la9041265
Parsons and Ninham
mined by Dagastine et al.43 and take mica as our surface, using the
dielectric model of Chan and Richmond.44 The excess polariz-
ability Ri* refers to the effective polarizability of the ion inside the
depolarizing medium of the solvent, and it is explained in more
detail below.
The water dielectric data were obtained in numerical form from
Dagastine et al.,43 with the static dielectric constant45 taken to be
ε = 78.36. The dielectric function for mica follows the model44
εuv - 1
εðiωÞ ¼ 1 þ ð10Þ
1 þ ðω=ω0 Þ2 þ ω=g
with εuv = 2.45, ω0 = 2.38  1016 rad s-1, and g = 4.89  1016
rad s-1. At zero frequency, the static dielectric constant of mica
was set to ε = 5.4.
Ab Initio Polarizabilities. Dynamic polarizabilities were
calculated using quantum chemical software Molpro.46 Electron
correlation is generally significant, especially for anions35 where
the correction due to electron correlation may be as much as 20-
50%. Electron correlation was handled using the coupled-cluster
single and double (CCSD) model. A total of 2100 frequency
points were calculated for each ion, from 0 to 1017 Hz, corre-
sponding to far UV/soft X-ray frequencies (around 5 nm in
wavelength). Dunning’s augmented correlation consistent basis
sets47 were used for smaller ions, nitrate, and water, namely, aug-
cc-pCVQZ for Be2þ and Mg2þ, aug-cc-pwCVQZ for nitrate, and
aug-cc-pCV5Z for water. Effective core potentials (pseudopoten-
tials) were applied to the heavier alkali earth ions Ca2þ through
Ra2þ, using the Stuttgart ECPnMDF family of basis sets.48
Although we use the full ab initio data in this paper, it may be
useful in other applications to have a parametrized analytic model
of the dynamic polarizability,
ð6Þ
X fj
RðiωÞ ¼ R0 ð11Þ
j 1 þ ðω=ωj Þ2
modal frequency, respectively, of each mode contributing to the
total dynamic polarizability. We have shown elsewhere35 that a
ð7Þ
single mode model provides a poor estimate of the polarizability,
particularly when the single modal frequency is derived from the
ionization potential of an ion. In the latter case, the modal
frequency is too low such that the frequency dependence of the
polarizability decays too rapidly. The strength of dispersion
energies is therefore underestimated. For anions, the error in
ð8Þ around 70%. It is less disastrous for metal cations at 20% error. A
multimode fit, on the other hand, is accurate to within 0.03% over
the entire frequency range. The multimode parametrization of the
ab initio polarizabilities is given in Table 1 for the alkali earth
cations together with the nitrate anion and the neutral water
ð9Þ
molecule. In the case of the latter polyatomic species, their
geometry was first optimized.
Ab initio calculations do provide the full anisotropic polariz-
ability tensor. Anisotropic effects are likely to be interesting for
(43) Dagastine, R. R.; Prieve, D. C.; White, L. R. J. Colloid Interface Sci. 2000,
231, 351–358.
(44) Chan, D.; Richmond, P. Proc. R. Soc. London, Ser. A 1977, 353, 163–176.
(45) CRC Handbook of Chemistry and Physics, 84th ed.; Lide, D. R., Ed.; CRC
Press: Boca Raton, FL, 2004.
(46) Werner, H.-J., et al. MOLPRO, a package of ab initio programs, version
2008.1; University College Cardiff Consultants Limited: Wales, UK, 2008; see http://
www.molpro.net.
(47) Woon, D. E.; Thom, H.; Dunning, J. J. Chem. Phys. 1995, 103, 4572–4585.
(48) Lim, I. S.; Stoll, H.; Schwerdtfeger, P. J. Chem. Phys. 2006, 124, 034107.
Langmuir 2010, 26(9), 6430–6436
Parsons and Ninham Article

Table 1. Static Polarizabilities, Weights, and Characteristic Frequencies for Multimode Decompositions of the Dynamic Polarizabilities of
Multivalent Cations, Nitrate Anion, and Neutral Water (See eq 11)a
mode 1 mode 2 mode 3 mode 4 mode 5
ion R0 (Å3) f1 ω1(a.u.) f2 ω2 (a.u.) f3 ω3 (a.u.) f4 ω4 (a.u.) f5 ω5 (a.u.)

Be2þ 0.0077 0.8291 4.8511 0.1710 9.9219

Mg2þ 0.0704 0.4259 4.1734 0.4881 2.3315 0.0860 8.9125
2þ
Ca 0.4692 0.5426 1.2095 0.4327 1.5398 0.0201 3.1135 0.0047 7.7725
2þ
Sr 0.8684 0.5510 0.9755 0.3575 1.1576 0.0003 1.4005 0.0912 3.3075
Ba2þ 1.5957 0.6963 0.7937 0.2718 1.0529 0.0306 1.8000 0.0012 5.5701
Ra2þ 2.0192 0.6052 0.7127 0.3531 0.9763 0.0408 1.7664 0.0010 5.8336
nitrate 5.0215 0.3418 0.2536 0.3863 0.5638 0.2270 1.0631 0.0429 2.4249 0.0018 9.3252
water 1.4255 0.0204 0.1906 0.5479 0.4669 0.4008 1.0286 0.0305 2.9532 0.0005 19.6298
a
1 a.u. = 6.57968  1015 Hz.

nonspherical ions such as the flat nitrate ion, especially in regard
to interactions with a flat interface. However, the model of
dispersion forces applied here (eqs 6 and 7) has assumed that
ions are spherical. The dispersion self-energies of anisotropic
ions21 and the ion-ion interactions of point charges with aniso-
tropic polarizabilities49,50 have been described, but a model of
ion-surface dispersion energies for nonspherical ions with finite
size has not yet been developed. We therefore apply a spherical
approximation to water and nitrate using mean isotropic polar-
izabilities.
Polarizabilities in Aqueous Solution. The effect of the water
medium on ion polarizabilities is handled in two ways. We
distinguish between the general effect of the bulk water medium
surrounding the ion and the specific effect of the water molecules
in the tightly held hydration layer.
Hydrated Ion. In the case of a tightly bound hydration layer,
the hydration water molecules are not quickly exchanged with the
bulk medium but are instead carried with the ion. In this case, the
hydration water molecules behave differently from water in the
bulk medium, partly due to their specific orientation around the
ion and partly due to the density of hydration shell, which will be
different from that of bulk water. This situation applies to the so-
called cosmotropic ions51-53 such as Liþ and multivalent ions
Mg2þ, Ca2þ, which are characterized by strong electric fields due
to either high charge or small size.
Effectively, the hydration water molecules become part of the
ion in such a way that the cosmotropic ion must be explicitly
treated as a hydrated ion. This means that the polarizability of the
hydration water molecules must be added to the polarizability of
the ion and the size of the ion must be increased by the width of the
hydration shell. These two hydration effects have competing
implications for the overall dispersion interactions of the hydrated
ion. The greater total polarizability tends to strengthen dispersion
energies, while the larger hydrated ion size tends to weaken them.
Applied to monovalent lithium and sodium ions, this hydration
model has found success in explaining ion specificity at silica
surfaces54 and in modeling the reversal of the Hofmeister series
observed experimentally at silica compared to alumina surfaces.55
The dominant component of dispersion energies arises from
the polarizability at optical/UV frequencies. Therefore, orienta-
tional effects of the hydration water molecules, corresponding to
(49) Imura, H.; Okano, K. J. Chem. Phys. 1973, 58, 2763–2776.
(50) Barash, Y. S.; Ginzburg, V. L. Sov. Phys. Usp. 1984, 27, 467–491.
(51) Collins, K. Biophys. Chem. 2006, 119, 271–281.
(52) Collins, K. D. Methods 2004, 34, 300–311.
(53) Collins, K. Biophys. J. 1997, 72, 65–76.
(54) Salis, A.; Parsons, D. F.; Bostr€om, M.; Medda, L.; Barse, B.; Ninham, B.
W.; Monduzzi, M. Langmuir, published online October 15, 2009, http://pubs.acs.org/
doi/abs/10.1021/la902721a.
(55) Parsons, D. F.; Bostr€om, M.; Maceina, T. J.; Salis, A.; Ninham, B. W.
Langmuir, published online November 4 2009, http://pubs.acs.org/doi/abs/10.1021/
la903061h.
Table 2. Hydration Numbers56 nw, Gaussian Radii10 a, and Dispersion
B Coefficients of Hydrated Cations and Nitrate at Mica Surface
ion nw a (Å) B (10-50Jm3)
Mg2þ 10 1.54 -3.69
Ca2þ 7 1.83 -3.74
Sr 2þ
6a
2.00 -3.49
Ba2þ 5 2.25 -2.91
nitrate n/a 2.01 -1.08
a
The hydration number of Sr2þ is the average of the Marcus56 values
for Ca2þ and Ba2þ.
microwave frequencies, are largely negligible. Thus, to a reason-
able approximation, the polarizability of the hydration shell is
determined simply by the density effect. That is, the polarizability
of the hydrated ion is taken to be the sum of the polarizability Ri of
the ion itself plus the polarizability Rw of the water molecules in
the hydration shell (nw in number). The hydrated polarizability of
a cosmotropic ion is then
Rhyd ðiωÞ ¼ Ri ðiωÞ þ nw Rw ðiωÞ ð12Þ
In this paper, we take the number of water molecules nw to be
given by experimental hydration numbers.56 The hydration
number of Sr2þ is not reported by Marcus,56 whose hydration
numbers we used for other ions. Experimental estimates of
hydration numbers vary57 but generally place the hydration
number of Sr2þ between that of Ca2þ and Ba2þ (but closer to
the former). For consistency with the Marcus hydration numbers
of Ca2þ and Ba2þ (7 and 5, respectively), we therefore assign an
hydration number of 6 to Sr2þ.
Hydrated ion radii are taken from Parsons and Ninham,10 with
the width of the hydration shell being added to the intrinsic hard
sphere radius of the ion. The hydration shell width is taken to be
one water radius, 1.14 Å (hard sphere radius). Hydration numbers
and Gaussian radii of the hydrated ions are given in Table 2. We
also list in Table 2 the dispersion B coefficients of the ions at mica
surface.
In accordance with Collins’ rule of matching water affinities,51,53
the procedure for the tightly bound hydration layer described here
is applied only to cosmotropic ions.21 Chaotropic ions such as
nitrate are considered to have a weakly bound hydration layer. It
seems reasonable to propose that hydration water molecules of
chaotropic ions are readily exchanged with the bulk medium. In
this case, the hydration shell does not need to be considered
explicitly. Rather, the hydration water molecules of chaotropic
ions are included within the normal bulk dielectric response of the
medium.
Bulk Depolarization: Excess Polarizability. When an ex-
ternal electric field polarizes an ion in solution, it also polarizes the
(56) Marcus, Y. Pure Appl. Chem. 1987, 59, 1093–1101.
(57) Hinton, J. F.; Amis, E. S. Chem. Rev. 1971, 71, 627–674.

Langmuir 2010, 26(9), 6430–6436 DOI: 10.1021/la9041265 6433

Article Parsons and Ninham

medium surrounding that ion. The polarized medium exerts a

depolarization field so that the local field experienced by the ion
differs from the external field. Treating the polarizable ion as a
dielectric sphere with permittivity εi, the polarization response of
the ion in solution may be described by an effective polariz-
ability35,58,59 R*,
i

 3Vi ½εi ðiωÞ - εw ðiωÞ

Ri ðiωÞ ¼ ð13Þ
4π ½εi ðiωÞ þ 2εw ðiωÞ

where εw is the dielectric function of the medium (water).

We describe the ionic permittivity via the simple relation εi =
1 þ 4πniRi = 1 þ 4πRi(iω)/Vi, where Vi is the ionic volume.10 This
simple formula is more robust to errors in the magnitude of the
ionic volume than the Clausius-Mossotti relation suggested Figure 1. Surface potential of calcium nitrate solution at mica
elsewhere.59,60 The latter may yield unphysical negative ionic surface as a function of electrolyte concentration. Experimental
dielectric values if the ionic volume has been underestimated. data15 (points) are compared against the theoretical curve (solid
The effective polarizability R*i obtained in this way is com- line).
monly referred to as the “excess polarizability”, since it is related
to the difference in the polarizability responses of ion and medium
(the “εi - εw” term in eq 13).
Note that the solvent has two effects on cosmotropic ions. First
the polarizability Rhyd of the hydrated ion is determined, that is,
the polarizability (in vacuum) of ion plus tightly held hydration
shell, eq 12. Then that hydrated ion polarizability is used to
determine the excess polarizability of the hydrated ion (eq 13).
The excess polarizability of a cosmotropic ion is not taken directly
from the ion’s intrinsic polarizability. In the case of chaotropic
ions, on the other hand, the excess polarizability is derived directly
from the intrinsic polarizability of the ion.

Results
Surface Potentials at a Mica Surface. The surface potential
of calcium nitrate solution at a mica surface is shown in Figure 1
as a function of electrolyte concentration. Experimental points15
are shown for comparison. The theoretical surface charge is taken
to be fixed at -0.012 C m-2, calibrated to fit to the experimental
data point at 10-3 M, measured at pH 5.9. The acidic conditions
at pH 5.9 have reduced the surface charge from the fully
dissociated surface charge of -0.33 C m-2 (1 site per 48 Å2)
due to protonation of the negatively charged surface sites. Our
fitted value of -0.012 C m-2 is consistent with the surface charge
of -0.022 C m-2 predicted by a charge regulation model19,61 at
pH 5.9 with a mica equilibrium constant pKH = 5.85, with the
surface potential taken in dilute solution at -70 mV.
Figure 1 shows excellent agreement between our theoretical
model and the experimental data at all concentrations. Notably,
the theoretical model is able to achieve charge reversal to the same
magnitude (þ12 mV at 0.1 M), and charge neutralization occurs
at the same concentration, 0.03 M, as observed experimentally.
Where the experimental data suggest a linear relationship
between the surface potential and log-concentration, it is curious
to observe a flattening in the theoretical curve at very high
concentrations. That is, the surface potential reaches an upper
limit at high concentration, corresponding to an asymptotic value
for the concentration of adsorbed Ca2þ at the surface. We show
the ratio of the concentration of Ca2þ at the surface to the bulk
concentration, as a function of bulk concentration, in Figure 2.
(58) Landau, L. D.; Lifshitz, E. M. Electrodynamics of Continuous Media;
Pergamon Press: Oxford, 1960; Vol. 8.
(59) Netz, R. R. Curr. Opin. Colloid Interface Sci. 2004, 9, 192–197.
(60) Boroudjerdi, H.; Kim, Y.-W.; Naji, A.; Netz, R.; Schlagberger, X.; Serr, A.
Phys. Rep. 2005, 416, 129–199.
(61) Miklavic, S. J.; Ninham, B. W. J. Colloid Interface Sci. 1990, 134, 305–311.
Figure 2. Relative surface concentration of adsorbed Ca2þ from
calcium nitrate at mica surface on a log scale as a function of bulk
concentration. The surface concentration [Ca2þ(surf)] is shown
relative to bulk concentration [Ca2þ(bulk)].
The surface concentration asymptotes to about 10 times the bulk
concentration. This asymptotic behavior is not observed experi-
mentally, since the highest reliably measured concentration is
0.1 M, with experimental measurements having poor reproduci-
bility at higher concentrations.15 The asymptotic behavior is
found at higher concentrations between 0.1 and 10 M. The charge
reversal effect is stronger with trivalent cations; in these systems,
the asymptotic surface potential at high concentrations can be
deduced experimentally from force measurements.62
Ion Specificity: Shift of Isoelectric Point. The Hofmeister
series in the alkali earth cations may be explored by considering
the surface potentials of nitrate solutions of these cations as a
function of salt concentration (Figure 3). In terms of the strength
of the charge reversal effect, we have Mg > Ca > Sr > Ba. The
isoelectric point (concentration of zero potential, or cvp) of each
solution is shifted accordingly, with Mg showing a zero potential
at the lowest salt concentration (0.003 M) and Ba2þ reaching zero
potential at the highest concentration (0.27 M). Ion specificity is
therefore strong, with the cvp’s changing by almost an order of
magnitude between cations, the full predicted set of cvp’s being
0.003, 0.024, 0.062, and 0.27 M for Mg, Ca, Sr, and Ba,
respectively.
The Hofmeister series seen in Figure 3 is consistent in three
ways. First, at any given concentration, the surface potentials
follow the series Mg > Ca > Sr > Ba. Second, the same series is
(62) Pashley, R. M. J. Colloid Interface Sci. 1984, 102, 23–35.

6434 DOI: 10.1021/la9041265 Langmuir 2010, 26(9), 6430–6436

Parsons and Ninham Article

Figure 3. Surface potential of alkali earth nitrate solutions at mica

surface as a function of electrolyte concentration.
found in the isoelectric points (concentrations of zero potential). Figure 4. Surface hydration. There is overlap of the hydrated
Third, the series is maintained in the asymptotic surface potentials layers of the surface and hydrated ions, while unhydrated ions
found at very high concentration. It is curious that the most are excluded from the surface hydration layer.
polarizable ion, Ba2þ, has the smallest charge reversal effect. This
Short range repulsion is weaker in Kþ solutions than in Naþ or
is chiefly due to ion hydration, with Ba2þ having the smallest
Ca2þ solutions, and Pashley cites the surface free energy of Kþ at
number of hydration waters and therefore the smallest hydration
below 1kT, in contrast to that of Naþ. The surface dispersion free
enhancement to the total polarizability of the hydrated ion. Mg2þ,
energy of an unhydrated Kþ ion using our B coefficient at z = 0,
conversely, is the least polarizable of the cations but exhibits the
however, is 2.5kT. That is, the surface energy of Kþ at contact is
largest charge reversal effect due to its greater number of hydra-
about the same as that of hydrated Naþ rather than being
tion waters.
significantly smaller.
Ion Adsorption and Secondary Hydration Forces. Pashley,
This contradiction may be resolved by applying the concept of
Israelachvili, and co-workers have measured surface forces be-
the hydration layer to the surface itself,67 complementary to the
tween two mica surfaces in solution.16,17,63,64 They found the
ionic hydration layer modeled in this paper. The hydrated ion
measured forces at close separations (10-40 Å) to be larger than
model has been applied to tightly hydrated cosmotropic ions such
expected from DLVO theory alone. Pashley interpreted these
as the divalent cations or Naþ. Kþ on the other is classified10,21 as
repulsive forces to be derived from the adsorption of hydrated
chaotropic with a weakly held hydration layer. We have here
ions and therefore labeled them “secondary hydration forces”.65,66
applied Collin’s criteria for distinguishing between cosmotropic
The repulsive force was attributed to the adsorption free energy of
and chaotropic ions, using Jones-Dole viscosity coefficients.51-53
hydrated ions to the surface. In the case of Ca2þ, for instance, the
Tightly hydrated cosmotropic ions are those with a positive
free energy of adsorption was estimated empirically17 at 4kT.
Jones-Dole viscosity coefficient, and weakly hydrated chaotro-
We have shown how ion-surface dispersion interactions
pic ions are those with a negative Jones-Dole coefficient. Among
provide an explanation for the phenomenon of surface charge
the group I alkali cations, the boundary is found between Naþ
reversal. The surface dispersion interaction provides additional
and Kþ, with Naþ having only a slightly positive Jones-Dole
adsorption beyond that expected from electrostatic interactions.
coefficient. The notion of surface-induced ion dehydration, which
It is instructive to consider the value of the ion-surface
√ dispersion
may for instance occur at alumina surfaces,55 may be relevant to
interaction at contact (z = 0), Ud0 = 16B/(3 πa3). This quantity
borderline cases such as Naþ. Applying Collin’s law of matching
may be interpreted as the adsorption energy of the ion. In the case
water affinities51,53,68 to the ion-surface interaction, there will be
of hydrated, Ca2þ its value is -10.98 kJ mol-1, or -4.4kT at room
a greater affinity for hydrated ions to approach the hydrated
temperature (T = 298 K). The closeness of the magnitude of this
surface. The hydration layers of ion and surface may overlap,
quantity to Pashley’s free energy, at 4kT, is certainly not coin-
bringing the center of the ion close to the edge of the surface
cidental. It seems apparent that ion-surface dispersion interac-
hydration layer, as illustrated by hydrated Ca2þ in Figure 4.
tions provide, or at the very least contribute substantially to, the
This brings insight into the physical meaning of ion-surface
mechanism for ion adsorption to the mica surface which leads to
contact at z = 0. Rather than suggesting by z = 0 that the ion is
Pashley’s short-range repulsive forces.
embedding into the mica surface itself, we may interpret z = 0 to
This interpretation is supported also by the ion-surface
correspond to the outer edge of the surface hydration layer, that
dispersion energies for monovalent cations.35 The surface disper-
is, to a distance of closest approach of the hydrated ion. Contact
sion energies of hydrated Liþ and Naþ may be calculated at
at z = 0 is defined by the surface hydration layer. This model also
-1.6kT and -2.6kT, respectively. These magnitudes are consis-
partly explains why the mica surface charge has been calibrated to
tent with Pashley’s adsorption energies16 which are likewise
-0.012 C m-2, slightly lower than the -0.022 C m-2 expected
greater than 1kT.
from mica at pH 5.9 under a charge regulation model (see above);
The argument that ion adsorption driven by dispersion forces
it is an effective charge accounting for the displacement of the
leads to Pashley’s short-range repulsion may be strengthened
surface hydration layer.
further by considering the repulsive force in Kþ electrolyte.16
As for Kþ, as a chaotropic, weakly hydrated ion, it cannot
penetrate into the surface hydration layer, also illustrated in
(63) Israelachvili, J. N. Adv. Colloid Interface Sci. 1982, 16, 31–47.
(64) Ducker, W. A.; Pashley, R. M. J. Colloid Interface Sci. 1989, 131, 433–439.
(65) Pashley, R. J. Colloid Interface Sci. 1981, 80, 153–162. (67) Johnson, S. B.; Franks, G. V.; Scales, P. J.; Healy, T. W. Langmuir 1999, 15,
(66) Pashley, R. M.; Israelachvili, J. N. J. Colloid Interface Sci. 1984, 101, 511– 2844–2853.
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Langmuir 2010, 26(9), 6430–6436 DOI: 10.1021/la9041265 6435

Article
Figure 4. Its surface dispersion energy should therefore be taken
at the distance of closest approach, one ionic radius out from z =
0, where the Kþ surface dispersion energy drops to - 0.5kT. In
this way, the behavior of Kþ is brought in line with Pashley’s
observations. The link between our ion-surface dispersion en-
ergy and Pashley’s short-range repulsive forces appears to be
consistent. The question of the effective surface charge and
location of z = 0 may be made more robust by explicitly adding
the surface hydration layer to the calculation. The relationship
between ionic dispersion forces and short-range repulsion be-
tween surfaces will be explored more closely in subsequent work.
Our model here does not allow for the extremely short-range
oscillatory forces reported by Pashley and Israelachvili.66 A
multilayer model of the surface hydration layers or spatial
structure in the solvent69,70 would be required to theoretically
model oscillatory forces.
The short-range repulsive forces have been termed as “hydra-
tion forces” by Pashley, which seems somewhat mislabeled
insofar as the repulsion is driven by adsorption due to dispersion
forces (“adsorption forces” might be more apt). However, given
the behavior of Kþ and the interpretation of its relationship to the
hydration layer of the surface, “hydration forces” is perhaps not
invalid. However, it should be understood to refer to hydration of
the surface as much as to hydration of the ions.
The agreement between Pashley’s calcium ion adsorption
energy and our surface dispersion energy, at around 4kT, is
interesting because both Pashley’s and our modeling are based
on a Poisson-Boltzmann description of the electrolyte which
neglects ion-ion correlations. The theoretical modeling of the
calcium nitrate experiments motivating this paper used the
anisotropic hypernetted chain (HNC) model by Kjellander and
Marcelja et al.,15,37 which does include ion-ion correlations but
neglects ionic dispersion interactions. The site binding model in
these HNC calculations took a slightly lower Ca2þ adsorption
energy, at 2.5kT. The effect of ion-ion correlations, aside from
other effects such as inducing spatial ordering between ions, is to
provide a limit to the ion concentration adsorbed at the surface by
preventing ions from crowding on top of each other. They
introduce a distance of closest approach to the ionic interactions.
As a consequence, Marcelja’s lower adsorption energy indicates
that ion-ion correlations prevent calcium ions, on average, from
approaching the surface hydration layer at z = 0. The calcium ion
surface dispersion energy falls back to 2.5kT at a distance of 0.73
Å from the surface, which, perhaps coincidentally, is close to the
radius of a bare (unhydrated) calcium ion. Our model of ionic
dispersion forces therefore again seems to be consistent with HNC
calculations that include site binding. That is, site binding in a
HNC model can explained by ionic dispersion interaction taken in
conjunction with the distances of closest approach that form part
of the ion-ion correlations of a HNC model. This approach has
been shown using model dispersion B coefficients to have an
impact on forces between surfaces,38 increasing or reducing them
depending on the value of B and surface charge density. Reports
(69) Basilevsky, M. V.; Parsons, D. F. J. Chem. Phys. 1998, 108, 9114–9123.
(70) Cherepanov, D. A. Phys. Rev. Lett. 2004, 93, 266104.
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University of Gothenburg, 2009, http://hdl.handle.net/2077/21040.
6436 DOI: 10.1021/la9041265
Parsons and Ninham
on charge reversal effects in a HNC model are forthcoming.71 The
ab initio polarizabilities reported here and previously35 can help
these more sophisticated HNC models achieve quantitative
agreement between theory and experiment, and come closer by
refining the B values used, just as they have improved agreement
with simple Poisson-Boltzmann theory.
Conclusion
By applying ab initio ionic polarizabilities with an hydration
model for alkali earth cations to a modified Poisson-Boltzmann
description of an electrolyte, we have been successful in reprodu-
cing charge reversal observed experimentally in surface potentials
at mica surfaces. Charge reversal appears due to increased ion
surface affinity driven by nonelectrostatic ion-surface dispersion
interactions (alongside ion correlation forces, not considered
here). This same mechanism appears to be responsible for
short-range repulsive forces (hydration forces) observed experi-
mentally.
We suggest that the idea of a hydration layer, applied here to
hydration of ions, should also be considered at surfaces. It seems
likely that a tightly bound surface hydration layer will be relevant
to some surfaces but not others, in the same way that cosmotropic
ions in solutions have a tightly held hydration layer while
chaotropic ions do not.
Ions were treated as spherical in this paper. We expect inter-
esting anisotropic effects may appear if a theory of nonspherical
ions is developed. This will introduce ion shape as a third element
of ion specificity, following ion size and ion polarizability, that
will contribute to the ion specific effects of planar ions such as
nitrate, formate, or carbonate, and linear ions such as the cyanate
series. Shape effects will likewise explain the specific behavior of
anisotropically hydrated ions such as hydroxide. Hydrated hy-
droxide forms a pyramid with water at the base and the ion at the
apex,72,73 which will impact on the affinity of hydroxide to a
surface. This kind of anisotropic hydrated system is best modeled
with explicit hydration waters, moving beyond the simple hydra-
tion model described in this paper.
The success found here in modeling charge reversal suggests
that the model of hydrated ions with dispersion forces may be
applicable to the exploration of ion surface effects at surfaces of
biological or medical interest. For instance, the lithium ion is used
in treating mood and bipolar disorders74,75 while cerium(III)
nitrate can be used in medication for burns.76 Is the bioeffective-
ness of these ions determined by their physical properties, through
the ion specific shift that they induce on the surface potentials of
cell membranes?
Acknowledgment. The authors would like to thank Stjepan
Marcelja for helpful and thought provoking discussions. We
acknowledge the assistance of the staff at the Australian National
Computational Infrastructure National Facility.
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