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PRL 103, 035701 (2009) PHYSICAL REVIEW LETTERS 17 JULY 2009

Ionic and Wigner Glasses, Superionic Conductors, and Spinodal Electrostatic Gels:
Dynamically Arrested Phases of the Primitive Model
L. E. Sánchez-Dı́az,1 A. Vizcarra-Rendón,2 and R. Juárez-Maldonado1
1
Instituto de Fı́sica ‘‘Manuel Sandoval Vallarta’’, Universidad Autónoma de San Luis Potosı́,
Álvaro Obregón 64, 78000 San Luis Potosı́, SLP, Mexico
2
Unidad Académica de Fı́sica, Universidad Autónoma de Zacatecas,
Paseo la Bufa y Calzada Solidaridad, 98600, Zacatecas, Zac., Mexico
(Received 16 February 2009; published 15 July 2009)
Based on the recently proposed self-consistent generalized Langevin equation theory of dynamic arrest,
in this letter we show that the ergodic-nonergodic phase diagram of a classical mixture of charged hard
spheres (the so-called ‘‘primitive model’’ of ionic solutions and molten salts) includes arrested phases
corresponding to nonconducting ionic glasses, partially arrested states that represent solid electrolytes (or
‘‘superionic’’ conductors), low-density colloidal Wigner glasses, and low-density electrostatic gels
associated with arrested spinodal decomposition.

DOI: 10.1103/PhysRevLett.103.035701 PACS numbers: 81.30.Dz, 64.70.P
, 81.05.Kf

A fluid of s species of electrically charged hard spheres
of diameter
i and charge qi , (i ¼ 1; 2; . . . ; s), present at
number concentration ni , and immersed in a uniform me-
dium of dielectric constant , is referred to as the primitive
model (PM) [1]. This model system provides a simple but
qualitatively accurate representation of a large number of
physically relevant systems, ranging from electrolyte, mac-
romolecular and micellar solutions to colloidal dispersions,
molten salts and classical plasmas. The interplay between
hard-sphere and Coulomb interactions gives rise to char-
acteristic universal features, including the purely hard-
sphere behavior expected at high temperatures and the
purely electrostatic, Debye-Hückel–like behavior, at low
total hard-sphere volume fractions and small electrostatic
couplings. In the regime of strong interactions (large total
volume fractions and/or low reduced temperatures), con-
densed equilibrium phases appear, including crystalline
solids and liquid phases such as molten salts [2,3]. In
addition to these equilibrium phases, dynamically arrested
states are also observed in real ionic systems, including
high density ionic glasses [4], low-density Wigner glasses
[5], and low-density electrostatic gels [6]. In this letter we
show that the occurrence of these arrested phases can be
expected on the basis of the interplay of only the hard-
sphere and the purely electrostatic interactions represented
by the PM above.
The fundamental understanding of dynamically arrested
states is a major challenge of contemporary statistical
physics and materials science [7–9]. Among the best es-
tablished theoretical approaches to their description, the
mode coupling theory (MCT) [10] stands out as the first-
principles theory with the highest quantitative predictive
power, whose most spectacular success is the prediction of
the reentrant glass transition in monodisperse colloidal
suspensions of particles with generic short-ranged attrac-
tive interactions [11,12]. A similar reentrant behavior has
been observed with sufficient detail, although in bi-
component dispersions of hard-sphere colloids with added
nonadsorbing polymer [13].
Although the bicomponent version of MCT applied to a
binary mixture model representation of the colloid-
polymer mixture fails to predict this experimentally-
observed reentrance [14], the bicomponent version of a
similar but alternative theory of dynamic arrest, referred to
as the self-consistent generalized Langevin equation
(SCGLE) theory [15], seems to explain satisfactorily the
main features of these experimental observations [16]. In
this letter we report the dynamic arrest scenario predicted
by the same theory when applied to electroneutral mixtures
of electrostatically charged particles modeled by the primi-
tive model above. The first study of this sort was carried out
by J. Bosse and collaborators a decade ago using MCT
[17,18]. The present study reveals, however, a richer and
physically more consistent glass transition phase diagram,
which clearly distinguishes between fully arrested non-
conducting glasses or gels and partially-arrested states
that represent fast ionic conductors or low-density colloi-
dal Wigner glasses.
The SCGLE theory of dynamic arrest leads to a remark-
ably simple equation for the longtime asymptotic value i
of the mean squared displacement of particles of species i,
i  limt!1 hð
RðiÞ Þ2 i. This property constitutes a par-
ticularly convenient order parameter to describe dynamic
arrest in mixtures, since it indicates in an unambiguous
manner if the particles of that species diffuse (i ¼ 1) or
pffiffiffiffiffi
are localized (finite value of i ). In the latter case, i is
the localization length of particles of species i. The re-
ferred equation reads [15]
1 1 Z 3 2 pffiffiffi
¼ d kk f½ þ k2 
1 gii fc nS½S
i 3ð2Þ3
pffiffiffi
þ k2 
1 nhgii ; (1)

0031-9007=09=103(3)=035701(4) 035701-1 Ó 2009 The American Physical Society

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PRL 103, 035701 (2009) PHYSICAL REVIEW LETTERS 17 JULY 2009
pffiffiffi 1

where S, h, c, , and n are s  s matrices, S being the

1
a) b)

matrix of partial static structure factors Sij ðkÞ of the 0.1 0.1
F-F
F-F

s-component mixture, h and c being the corresponding

T*
T*
F-G
Ornstein-Zernike pffiffiffi matrices of total and pffiffiffi direct correlation
pffiffiffiffiffi 0.01 0.01

functions [1], n being defined as ½ nij  ij ni , and G-G

G-G

ðkÞ being a diagonal matrix given by ij ðkÞ ¼ ij ½1 þ 0.001

1e-05 0.0001 0.001 0.01 0.1
0.001
1e-05 0.0001 0.001 0.01 0.1 1

ðk=kcðiÞ Þ2 
1 , where kcðiÞ is the location of the first minimum

φ φ

following the main peak of Sii ðkÞ [15]. For a given system c)
1
F-F
d)
1
F-G

one first determines Sij ðkÞ, as well as the matrices c, h, and

, and then numerically solve the s equations for the s 0.1

F-G
0.1
F-F

T*
parameters i to classify the resulting state. For example,
for a binary electrolyte, the solution 1 ¼ 2 ¼ 1 corre- 0.01 0.01 G-F

sponds to a fully ergodic fluid state (an ionic solution or a G-G G-G

0.001 0.001
molten salt), whereas a finite solution for both of these 1e-05 0.0001 0.001
φ
0.01 0.1 1 1e-05 0.0001 0.001 0.01 0.1 1

parameters corresponds to a fully arrested state, in which 1 1

e) f) F-G
both ionic species are immobilized. At large size- and/or
F-F
valence-asymmetries we may also expect regions of mixed 0.1 0.1

states in which one ionic species is arrested, while the other G-F

T*

T*
ionic species remains mobile (finite 1 but 2 ¼ 1, or vice
0.8 1 1
1

D(L)α /D0
0.6 0.1

D(L)α /D0
0.01 0.01 2
G-G 0.4 0.01
versa). 0.2
0
2

0 0.05 0.1 0.15 0.2

0.001
0.0001
0.04 0.2
We have scanned the state space of the primitive model 0.001
1e-05 0.0001 0.001 0.01 0.1 1
0.001
1e-05
T
0.0001
*
0.001 0.01
T*
0.1 1

to determine the regions where these dynamic states occur, φ φ

and the boundaries between them, in the manner reported

in Ref. [15] for the binary hard-sphere mixture. In the
present case we base this first scanning on Blum’s solution
of the mean spherical approximation (MSA) for the static
structure factors of the PM using the analytic expressions
summarized by Hiroike [19]. Notice that in the high tem-
perature limit we recover the Percus-Yevick (PY) static
structure factors of the binary uncharged hard-sphere mix-
ture studied in [15]. For concreteness, let us consider a PM
binary electrolyte, s ¼ 2. This generic system is specified
by its size- and charge-asymmetry described, respectively,
by  
1 =
2 and  
q1 =q2 . Because of charge neu-
trality (n1 q1 þ n2 q2 ¼ 0), the macroscopic states of this
system can be defined with only two control parameters,
for which we choose the total volume fraction  ¼ 1 þ
2 ð ðn1
31 þ n2
32 Þ=6Þ and a reduced temperature
T   kB T
12 =jq1 q2 j, with
12  ð
1 þ
2 Þ=2.
Figure 1 presents a sequence of illustrative results for the
dynamic arrest phase diagram of the primitive model. The
solid line in Fig. 1(a) is the SCGLE glass transition line of
the symmetric (q1 ¼
q2 ) restricted (
1 ¼
2 ) primitive
model (RPM). Above and to the left of this line the system
is fully ergodic, i.e., both species remain fluid (FF),
whereas to the right and below this line the system is fully
arrested, i.e., the particles of both species are localized
(‘‘glass-glass’’ states, denoted as GG). Thus, we see that at
high temperatures the glass transition volume fraction
essentially coincides with that of the hard-sphere system,
g  gðHSÞ (0:537 in the SCGLE theory within the PY
approximation). As the temperature and volume fraction is
lowered, however, the almost vertical transition line bends
to the left, and becomes almost horizontal, exhibiting a
mild maximum at   0:01. At still lower volume frac-
FIG. 1 (color online). Dynamic arrest phase diagram of the
binary primitive model in the state space (T  ,  calculated with
MSA [(a)–(e)] and GMSA (f) partial static structure factors for
various combinations of the size- and charge-asymmetry pa-
rameters  and : (a)  ¼ 1,  ¼ 1; (b)  ¼ 1,  ¼ 1=3;
(c)  ¼ 1,  ¼ 1=20; (d)  ¼ 1=5,  ¼ 1; (e)  ¼ 1=20,  ¼
1. The labels FF and GG, indicate, respectively, fully ergodic and
fully arrested states. In the mixed states labeled FG in (b),(c), and
(f), the more highly charged ions form a glass and the less
charged ions remain mobile. In the regions labeled GF in (d) and
(e), the smaller ions form a glass and the larger ions remain
mobile. Solid lines thus indicate the boundary of the fully
arrested region GG and dashed lines indicate the boundary of
the fully ergodic region FF. The green dotted line in (f) is the
spinodal curve, and the soft dark, thick red and thick blue curves
(both, solid and dashed) correspond to the systems in (a),(b), and
(c), respectively. The left side inset shows the extrapolation
(lines) of the long-time self-diffusion coefficients (points) D1ðLÞ
and DðLÞ 
2 as a function of T for fixed  ¼ 0:1. The right-side
inset is the logarithmic version.
tions it is approximated by g  ðconstÞTg3 . These results
are quite similar to those of MCT [17], also plotted in
Fig. 1(a) for comparison (dash-dotted line).
For symmetry reasons, the simultaneous dynamic arrest
of both ionic species is the only possible transition from
fully ergodic to fully arrested states in the symmetric RPM
just discussed. As soon as this perfect symmetry is broken
by charge- or size-asymmetries, the possibility of dynami-
cally mixed states appear. For a given binary system there
are two such possibilities, one in which the first species
remains fluid and the second becomes a glass (denoted as
FG) and the opposite case (GF). Thus, Fig. 1(b) presents

035701-2

PRL 103, 035701 (2009) PHYSICAL REVIEW LETTERS
the results for a size-symmetric ( ¼ 1) but charge-
asymmetric 1–3 electrolyte ( ¼ 1=3), which now exhibits
a region of (FG) dynamically mixed states, in which the
ions of higher valence become localized, and their mono-
valent counterions remain mobile. This is a conceptually
very interesting prediction of the SCGLE theory, since it
implies the possibility of finite ionic conductivity of the
delocalized counterions through the disordered solid ma-
trix of the arrested ionic species. These mixed states thus
describe solid electrolyte (or superionic) conducting
phases. To our knowledge, this is the first time that a
prediction of this sort derives from a ‘‘first-principles’’
theory such as MCT or the present SCGLE theory, for a
simple but well-defined model of an ionic system. The
sequence of Figs. 1(a)–1(c) illustrates that this effect be-
comes more important as the charge-asymmetry increases
from  ¼ 1 to 1=3 to 1=20. The latter case [Fig. 1(c)] is, of
course, rather unrealistic, since it corresponds to a solution
of macroions (valence 20) of the same size as its mono-
valent counterions. Nevertheless, it serves to illustrate a
limiting condition in which, upon lowering the reduced
temperature at low fixed volume fraction, the highly
charged macroions first become dynamically arrested
forming a Wigner glass, with the mobile counterions pro-
viding a Debye-Hückel–like screening, and in which at still
lower temperatures also the counterions are predicted to
localize, thus resulting in a nonconducting low volume
fraction disordered ionic solid. We conjecture that the latter
dynamic phase is of a similar nature as the low volume
fraction gels formed by certain clays like Laponite (leaving
aside, of course, the disklike shape of these macroions).
Other fascinating predictions of the SCGLE theory
arise as size-asymmetries are considered. This is illustrated
in Fig. 1(d), which corresponds to a charge-symmetric
( ¼ 1) but size-asymmetric ( ¼ 1=5) system. In this
system we observe two regions of mixed states. At high
temperatures and large volume fractions, a small region
appears (labeled FG) in which the smaller ions are de-
localized while the larger ions are arrested. This region
corresponds to the mixed states already discussed for
neutral hard spheres [15], and disappears at lower tem-
peratures at a bifurcation point where its two border tran-
sition lines merge into a single glass transition line corre-
sponding to the simultaneous arrest of both ionic species.
This line in its turn bifurcates again at lower temperatures
and volume fractions, giving rise to a second region of
mixed states labeled GF. The two transition lines bordering
this region merge at still lower volume fractions in another
glass transition line from fully ergodic to fully arrested
states.
At first glance, the nature of this second region of mixed
states [labeled GF in Fig. 1(d)] might seem rather counter-
intuitive since it implies the possibility that in these elec-
trostatically driven mixed states of a binary charge-
symmetric electrolyte, the larger ions would be the con-
035701-3
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ducting species, and the smaller-sized ions would form the
disordered arrested matrix of a Wigner glass. This, how-
ever, is a pretty robust prediction, as illustrated in Fig. 1(e),
in which we observe that increasing the size asymmetry
even further (to  ¼ 1=20), the size of this region increases
considerably.
There are, of course, many structural and dynamic prop-
erties of the various glassy phases just discussed, which
must be studied at the level of detail provided by the full
solution of the SCGLE theory, and this is the subject of an
ongoing systematic and thorough research program [20].
The most elementary information on these dynamic
phases, however, is the very statement of their existence
and the determination of the state space region where they
should be expected to appear. This is the information
contained in the dynamic arrest phase diagrams just dis-
cussed which are, hence, the dynamic analog of the ordi-
nary thermodynamic equilibrium phase diagrams. While
the relationship between these two categories of phase
diagrams must still be understood on more fundamental
grounds, in the present case the SCGLE theory reveals a
striking relationship between them, as we now discuss with
the results illustrated in Fig. 1(f).
One of the main drawbacks of the MSA approximation
is its poor thermodynamic consistency. A particular con-
sequence of this limitation is that the thermodynamic
properties of this system, calculated through the com-
pressibility route, does not predict a gas-liquid phase tran-
sition, although such transition is predicted if the energy
route is employed [21]. Fortunately, a thermodynamically
consistent version, referred to as the generalized mean
spherical approximation (GMSA), exists for the restricted
primitive model (RPM,  ¼ 1) [22]. Within this approxi-
mation, both routes predict the equilibrium gas-liquid
phase transition, whose spinodal curve is shown as the
(green) thick dotted line in Fig. 1(f). This curve is inde-
pendent of charge-asymmetries when plotted in terms of
the reduced variables (, T  ) employed in the figure (we
should stress, however, that such scaling is specific to the
MSA and GMSA approximations [23], and might not be
confirmed by more accurate approximations).
We have recalculated the dynamic arrest phase diagrams
of the (charge-asymmetric) RPM using the thermodynami-
cally consistent GMSA partial static structure factors, and
the results of these improved calculations are illustrated in
Fig. 1(f) for the systems considered in Figs. 1(a)–1(c). The
first striking feature to notice is that the region GG of fully
arrested states in the low T  -low  regime, whose MSA
boundary [dark solid lines in Figs. 1(a)–1(c)] exhibits a
mild maximum at   0:1, is now predicted to be clearly
related to the gas-liquid coexistence curve of the PM in
both, symmetric and charge-asymmetric systems. In fact,
in the vapor side these dynamic arrest lines seem to be
independent of the charge asymmetry and to preempt the
spinodal region, whereas at volume fractions above the

PRL 103, 035701 (2009) PHYSICAL REVIEW LETTERS
critical point they seem to follow the spinodal curve, and
even to get slightly inside the spinodal region, as indicated
by the thin dotted lines inside this region. Because of the
lack of solutions of the GMSA inside the spinodal region,
the latter segments of the dynamic arrest lines were not
determined through the use of Eq. (1). Instead, we deter-
mined the long-time self-diffusion coefficients DðLÞ 1 and
DðLÞ
2 of the two ionic species for values of T 
and  outside
the spinodal and extrapolated these results to the interior of
the spinodal region, as illustrated in the inset of Fig. 1(f).
The points are calculated with the SCGLE theory and the
line is the best extrapolation, in the sense that all points are
fitted. The dotted segment of the dynamic arrest line inside
the spinodal curve is the locus of the points where the
extrapolated value of these alternative order parameters
ceased to have a finite value.
The results illustrated in Fig. 1(f) constitute a very
dramatic prediction, since they imply, among other things,
that the gas-liquid spinodal decomposition of quenched
binary molten salts (such as alkali halides) might be dy-
namically arrested, very much in the same manner as it has
very recently been observed in colloidal dispersions of
oppositely charged colloidal particles [24] and in (non-
Coulombic) colloid-polymer mixtures [25]. Another rele-
vant conclusion illustrated by this figure is the confirmation
by the improved GMSA calculations of the existence of
regions of mixed states (bordered by a solid and a dashed
line), first predicted by the mean spherical approximation,
even though now their size is definitely smaller than in
Figs. 1(b) and 1(c). This means that the simpler MSA
calculations may be a useful devise for a first qualitative
exploration of the topology of the dynamic arrest phase
diagram of more complex ionic systems, including multi-
component ionic mixtures with electrostatically inert
(hard-sphere) components. Although we believe that this
is a rather general conclusion, the nonavailability of an
analytic solution of the GMSA for the size-asymmetric PM
prevents us from extending these conclusions to the con-
ditions illustrated in Figs. 1(d) and 1(e). Let us finally
mention that the solution of the entire time and wave vector
dependence of the full SCGLE system of equations yields
all the detailed information of the process of dynamic
arrest. The full analysis of these theoretical results, how-
ever, will be reported separately.
This work was supported by the Consejo Nacional de
Ciencia y Tecnologı́a (CONACYT, México) through grants
No. C02-44744, No. 84076, and FOMIX-SLP-107549. The
035701-4
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authors are deeply grateful to M. Medina Noyola and
P. Ramı́rez González for fruitful discussions.
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