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**substitutionally ordered solid phases from a binary mixture of oppositely
**

charged colloidal suspensions

Ganeshprasad Pavaskar and Sudeep N. Punnathanam

Citation: J. Chem. Phys. 138, 174504 (2013); doi: 10.1063/1.4802784

View online: http://dx.doi.org/10.1063/1.4802784

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THE JOURNAL OF CHEMICAL PHYSICS 138, 174504 (2013)

Determination of favorable inter-particle interactions for formation

of substitutionally ordered solid phases from a binary mixture

of oppositely charged colloidal suspensions

Ganeshprasad Pavaskar and Sudeep N. Punnathanam

a)

Department of Chemical Engineering, Indian Institute of Science, Bangalore, Karnataka 560012, India

(Received 23 January 2013; accepted 10 April 2013; published online 1 May 2013)

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either

substitutionally ordered or substitutionally disordered depending on the nature and strength of in-

teractions among the particles. In this work, we use Monte Carlo molecular simulations along with

the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the

formation of substitutionally ordered crystalline phases from a ﬂuid phase. The inter-particle inter-

actions are modeled using the hard core Yukawa potential but the method can be easily extended

to other systems of interest. The study obtains a map of interactions depicting regions indicating

the type of the crystalline aggregate that forms upon phase transition. © 2013 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4802784]

I. INTRODUCTION

Colloidal suspensions consisting of a mixture of oppo-

sitely charged particles have been shown to self-assemble into

crystalline substitutionally ordered solid phases.

1–7

Materials

made from such substitutionally ordered crystalline aggre-

gates ﬁnd potential applications in many technologies such

as photonics, catalysis, sensing, plasmonics, etc.

6, 8–10

They

display novel chemical or physical properties that are differ-

ent from those of individual particles. These properties can be

tuned through a suitable selection of materials for each type

of particle and also through variation in the properties of in-

dividual particles such as their size, shape, etc.

7, 11–13

For a given set of colloidal particles, the structures of

the crystalline aggregates strongly depend on factors such as

composition of the ﬂuid phase, charge screening, and charge

asymmetry. This dependence has been exploited by many

researchers to synthesize crystalline aggregates of various

structures. Bartlett and Campbell

1

and Leunissen et al.

7

have synthesized three-dimensional superlattices from a bi-

nary mixture of equal-sized but oppositely charged colloids

through self-assembly. In both these studies, the magnitude

and the sign of the charges on the particles were manipulated

through variation of salt concentration in the solvent medium.

The salt concentration also affects the magnitude of the De-

bye screening length. Weakly charged particles at high vol-

ume fractions self-assembled into a random hexagonal close

packed (rhcp) structure.

1

However, by suitably ﬁne tuning the

inter-particle interactions, both groups were able to synthe-

size superlattices with structures analogous to CsCl and NaCl

crystals. Leunissen et al.

7

also successfully synthesized super-

lattices from unequal-sized colloidal particles. Self-assembly

of binary mixtures consisting of metallic and semi-conductor

particles with sizes in the nanometer regime were performed

a)

Author to whom correspondence should be addressed. Electronic mail:

sudeep@chemeng.iisc.ernet.in

by Shevchenko et al.

12

and Kalsin et al.

6

In these studies too,

self-assembly of superlattices were achieved only after suit-

ably ﬁne-tuning the inter-particle interactions such as charge

screening and charge asymmetry. The synthesis of superlat-

tices through self-assembly would be greatly assisted by a

map of interactions depicting regions of stability of various

crystal structures.

From a theoretical standpoint, the formation of crys-

talline aggregates from colloidal suspensions is equivalent to

a ﬁrst-order ﬂuid to solid phase transition. This enables ap-

plication of techniques to compute phase equilibria towards

study of formation of these crystalline aggregates. In a recent

work by Pavaskar, Sharma, and Punnathanam,

14

the solid-

ﬂuid phase diagrams of a binary mixture of equal sized and

oppositely charged colloidal particles were computed using

Monte Carlo molecular simulations. The particle interactions

were modeled using the hard-core Yukawa potential. Under

the conditions studied, the system showed two types of solid

phases: a substitutionally ordered crystalline phase having a

body-centered cubic structure analogous to CsCl and a sub-

stitutionally disordered face-centered cubic (FCC) structure.

In general, the CsCl phase was favored when the ﬂuid con-

sisted of equimolar or close to equimolar amounts of oppo-

sitely charged particles whereas the FCC phase was favored

when one of the components exceeded the other by a large

amount. At an intermediate ﬂuid composition, there exists a

triple point where the ﬂuid, CsCl, and FCC phases are in equi-

librium. For a particular temperature or pressure, the location

of the triple points gives the composition range for the forma-

tion of the substitutionally ordered CsCl phase from a ﬂuid.

The location of the triple point is affected by various factors

such as temperature, charge asymmetry, and charge screening.

The study by Pavaskar, Sharma, and Punnathanam

14

revealed

that the composition range is highest when the magnitude of

the charges are equal and decreases sharply with the intro-

duction of charge asymmetry. For highly charge asymmet-

ric mixtures, the phase transition only gives substitutionally

0021-9606/2013/138(17)/174504/7/$30.00 © 2013 AIP Publishing LLC 138, 174504-1

174504-2 G. Pavaskar and S. N. Punnathanam J. Chem. Phys. 138, 174504 (2013)

disordered FCC phase. The study

14

also revealed the exis-

tence of an optimum range of charge screening that favored

the formation of CsCl phase.

The pressure-composition phase diagrams computed by

Pavaskar, Sharma, and Punnathanam

14

was at a single temper-

ature and for speciﬁc values of charge screening and charge

asymmetry. In this article, we extend those calculations of

solid-ﬂuid phase equilibria to determine the range of con-

ditions that favor the formation of substitutionally ordered

crystalline phases such as CsCl phase. We speciﬁcally de-

termine the triple point between the CsCl phase, the FCC

phase, and the ﬂuid phase with equimolar composition. The

triple point represents the boundary between conditions that

favor CsCl versus those that favor FCC phase. The variation

of the triple point is then computed across various value of

charge screening, charge asymmetry, and temperature using

Kofke’s method of Gibbs-Duhem integration.

15, 16

The ﬁnal

result is a map of interactions depicting regions indicating the

type of the crystalline aggregate that forms upon phase tran-

sition. In addition to ﬂuid-CsCl phase transition, the possibil-

ity of the ﬂuid phase crystallizing into other substitutionally

ordered phases was also studied. These included crystalline

phases analogous to CuAu, NaCl, and face-centered tetrago-

nal phase. However, within the conditions studied, either the

ﬂuid-CsCl or the ﬂuid-FCC phase transition was the most sta-

ble. We also studied the possibility formation of the Cu

3

Au

phase from a ﬂuid with mole fraction of 0.25 and 0.75 of one

of the particles. Again, within the conditions studied, only the

ﬂuid-FCC phase transition was stable.

II. MODEL

The system is a binary mixture of oppositely charged

spherical colloidal particles. We denote one of the compo-

nents of the mixture as A and the other one as B. Both types

of particles are equal-sized with a diameter of σ. The interac-

tions between colloidal particles are modeled using the hard-

core Yukawa interaction. This potential is deﬁned as

u

_

r

ij

_

=

⎧

⎨

⎩

Z

i

Z

j

e

−κ

(

r

ij

−σ

)

r

ij

/σ

if r

ij

σ

∞ if r

ij

< σ

, (1)

where u is the inter-particle potential energy, r

ij

is the distance

between particles i and j, and κ is the inverse screening length.

The variables Z

i

and Z

j

are the scaled charges on particles i

and j, respectively. The scaling is with respect to the charge

having the highest magnitude. In this study the value of Z

A

is

kept equal to unity and Z

B

is varied between 0 and −1. The

variable represents the energy when two like particles with

charges having magnitude equal to unity are in contact with

each other. For clarity, we introduce a new variable, α, that is

deﬁned to be the ratio of the charge on particle B to that of

particle A, i.e., α = Z

B

/Z

A

.

III. GIBBS-DUHEM INTEGRATION

For a system of oppositely charged particles, the proper-

ties that can be easily tuned are charges on particles and the

extent of electrostatic screening. This is equivalent to varia-

tion of the reduced variables T

∗

(=k

B

T/), κσ, and α, where

T is the temperature and k

B

is the Boltzmann constant. In

Ref. 14, it was observed that for T

∗

= 1.0 and α = −1,

the equimolar ﬂuid crystallized into the CsCl phase when

κσ = 6.0 and into FCC phase when κσ → ∞. Hence at

a deﬁnite value of κσ > 6.0, all the three phases will be in

equilibrium. When κσ is larger than this particular value, the

ﬂuid is in equilibrium with FCC phase and at lower values the

ﬂuid is in equilibrium with the CsCl phase. The location of

the triple point depends on the value of T

∗

, κσ, and α.

Our aim is to trace the locus of triple points as a function

of T

∗

, κσ, and α using Kofke’s method of Gibbs-Duhem

integration.

15, 16

The derivations of the differential equations

required for the Gibbs-Duhem integration are as follows.

A. Variation of chemical potential

and molar Gibbs free energy

The chemical potential, μ of a component in the ﬂuid or

FCC phase is a function of temperature, pressure, composi-

tion, charge ratio, and charge screening, i.e.,

dβμ

A

=

_

∂βμ

A

∂T

_

P,κσ,α,x

A

dT +

_

∂βμ

A

∂P

_

T,κσ,α,x

A

dP

+

_

∂βμ

A

∂κσ

_

T,P,α,x

A

dκσ

+

_

∂βμ

A

∂α

_

T,P,κσ,x

A

dα +

_

∂βμ

A

∂x

A

_

T,P,κσ,α

dx

A

,

(2)

dβμ

B

=

_

∂βμ

B

∂T

_

P,κσ,α,x

A

dT +

_

∂βμ

B

∂P

_

T,κσ,α,x

A

dP

+

_

∂βμ

B

∂κσ

_

T,P,α,x

A

dκσ

+

_

∂βμ

B

∂α

_

T,P,κσ,x

A

dα +

_

∂βμ

B

∂x

A

_

T,P,κσ,α

dx

A

,

(3)

where β =1/k

B

T, P is the pressure, and x

A

is the mole fraction

of component A. For a binary system, the chemical potentials

can be written in terms of the molar Gibbs free energy, G, as

μ

A

= G+(1 −x

A

)

_

∂G

∂x

A

_

T,P,κσ,α

,

μ

B

= G−x

A

_

∂G

∂x

A

_

T,P,κσ,α

.

Substitution of these identities in the Eqs. (2) and (3) fol-

lowed by application of thermodynamic relations results in

the following equations:

dβμ

A

= H

A

dβ +βV

A

dP +βW

A

dκσ +βY

A

dα

+(1 −x

A

)

_

∂μ

∂x

A

_

T,P,κσ,α

dx

A

, (4)

174504-3 G. Pavaskar and S. N. Punnathanam J. Chem. Phys. 138, 174504 (2013)

dβμ

B

= H

B

dβ +βV

B

dP +βW

B

dκσ +βY

B

dα

−x

A

_

∂μ

∂x

A

_

T,P,κσ,α

dx

A

, (5)

where H is the molar enthalpy, V is the molar volume,

W = (∂G/∂κσ)

T,P,α,x

A

, Y = (∂G/∂α)

T,P,κσ,x

A

, and μ

= μ

A

− μ

B

. In these equations, the overline indicates partial

molar property of a component.

The substitutionally ordered CsCl phase has an invariant

composition. Similar to the above derivation, the variation of

the molar Gibbs free energy for the CsCl phase is obtained as

dβG = Hdβ +βVdP +βWdκσ +βYdα. (6)

B. Two-phase equilibrium

The criteria for phase equilibriumbetween the ﬂuid phase

and FCC phase are

μ

(l)

A

= μ

(s)

A

,

μ

(l)

B

= μ

(s)

B

,

where the superscripts l and s represent the ﬂuid phase and

the FCC phase, respectively. If the ﬂuid composition is kept

ﬁxed then, upon substitution from Eqs. (4) and (5) followed

by elimination of x

s

A

we have

H

(l−s)

dβ +βV

(l−s)

dP +βW

(l−s)

dκσ +βY

(l−s)

dα = 0,

(7)

where

H

(l−s)

= x

(s)

A

_

H

(l)

A

−H

(s)

A

_

+x

(s)

B

_

H

(l)

A

−H

(s)

A

_

= (H

(l)

−H

(s)

) +

_

x

(s)

A

−x

(l)

A

_

_

∂H

(l)

∂x

(l)

A

_

T,P

,

V

(l−s)

= x

(s)

A

_

V

(l)

A

−V

(s)

A

_

+x

(s)

B

_

V

(l)

A

−V

(s)

A

_

= (V

(l)

−V

(s)

) +

_

x

(s)

A

−x

(l)

A

_

_

∂V

(l)

∂x

(l)

A

_

T,P

,

W

(l−s)

= x

(s)

A

_

W

(l)

A

−W

(s)

A

_

+x

(s)

B

_

W

(l)

A

−W

(s)

A

_

= (W

(l)

−W

(s)

) +

_

x

(s)

A

−x

(l)

A

_

_

∂W

(l)

∂x

(l)

A

_

T,P

,

Y

(l−s)

= x

(s)

A

_

Y

(l)

A

−Y

(s)

A

_

+x

(s)

B

_

Y

(l)

A

−Y

(s)

A

_

= (Y

(l)

−Y

(s)

) +

_

x

(s)

A

−x

(l)

A

_

_

∂Y

(l)

∂x

(l)

A

_

T,P

.

The criteria for equilibrium between the ﬂuid phase and the

CsCl phase is given as

G

(c)

=

μ

(l)

A

+μ

(l)

B

2

,

where the superscript c represents the CsCl phase. Again

keeping the ﬂuid composition ﬁxed, upon substitution from

Eqs. (4)–(6) we have

H

(l−c)

dβ +βV

(l−c)

dP +βW

(l−c)

dκσ +βY

(l−c)

dα = 0,

(8)

where

H

(l−c)

= (H

(l)

−H

(c)

),

V

(l−c)

= (V

(l)

−V

(c)

),

W

(l−c)

= (W

(l)

−W

(c)

),

Y

(l−c)

= (Y

(l)

−Y

(c)

).

C. Three-phase equilibrium

Equations (7) and (8) give the loci of points correspond-

ing to the ﬂuid-FCC phase equilibrium and ﬂuid-CsCl phase

equilibrium, respectively. The degree of freedom for the two-

phase equilibrium is three. The intersection of these loci gives

the three phase equilibrium between the ﬂuid, FCC, and CsCl

phase with the degree of freedom equal to two. The equations

determining the three-phase equilibrium are as follows.

Eliminating T from Eqs. (7) and (8) we get

(V

(l−s)

H

(l−c)

−V

(l−c)

H

(l−s)

)dP

+(W

(l−s)

H

(l−c)

−W

(l−c)

H

(l−s)

)dκσ

+(Y

(l−s)

H

(l−c)

−Y

(l−c)

H

(l−s)

)dα = 0. (9)

Eliminating P from Eqs. (7) and (8) we get

(H

(l−s)

V

(l−c)

−H

(l−c)

V

(l−s)

)dβ

+β(W

(l−s)

V

(l−c)

−W

(l−c)

V

(l−s)

)dκσ

+β(Y

(l−s)

V

(l−c)

−Y

(l−c)

V

(l−s)

)dα = 0. (10)

Eliminating κσ from Eqs. (7) and (8) we get

(H

(l−s)

W

(l−c)

−H

(l−c)

W

(l−s)

)dβ

+β(V

(l−s)

W

(l−c)

−V

(l−c)

W

(l−s)

)dP

+β(Y

(l−s)

W

(l−c)

−Y

(l−c)

W

(l−s)

)dα = 0. (11)

Eliminating α from Eqs. (7) and (8) we get

(H

(l−s)

Y

(l−c)

−H

(l−c)

Y

(l−s)

)dβ

+β(V

(l−s)

Y

(l−c)

−V

(l−c)

Y

(l−s)

)dP

+β(W

(l−s)

Y

(l−c)

−W

(l−c)

Y

(l−s)

)dκσ = 0. (12)

D. Computation of properties

The equations derived for the Gibbs-Duhem integration

are ﬁrst order differential equations. The quantities on the

right hand side of the differential equation are computed us-

ing simulations. These simulations for the ﬂuid phase and

substitutionally disordered FCC phase are carried out in the

isothermal-isobaric semi-grand ensemble (constant N, P, T,

μ) and those for substitutionally ordered CsCl phase were

done in the isothermal-isobaric ensemble (constant N, P, T).

The quantities that need to be calculated during Gibbs-Duhem

integration include H, V, W, and Y. These are calculated as

174504-4 G. Pavaskar and S. N. Punnathanam J. Chem. Phys. 138, 174504 (2013)

follows:

H = U +PV,

W =

_

∂U

∂κσ

_

,

Y =

_

∂U

∂α

_

,

where U is the potential energy of the system. In addition,

the computation of the partial molar properties in the ﬂuid

and FCC phases requires computation of the derivatives of H,

V, W, and Y. These are easily computed in the semi-grand

ensemble using the ﬂuctuation theory as follows:

_

∂H

∂x

A

_

T,P

=

Hx

A

−Hx

A

_

x

2

A

_

−x

A

2

. (13)

Similar equations can be used to compute partial derivatives

for V, W, and Y with respect to x

A

.

IV. RESULTS AND DISCUSSION

The application of the Gibbs-Duhem method requires an

a priori calculation of one coexistence point. In this study, the

starting point for the Gibbs-Duhem integration is the ﬂuid-

FCC and ﬂuid-CsCl coexistence point. The composition of

ﬂuid phase is x

A

= 0.5. The equilibrium is computed for con-

ditions T

∗

= 1.0, α = −1.0, and κσ = 3.0. The method

for computation of the phase equilibrium is similar to that

described in Ref. 14. The Monte Carlo simulations in the

isothermal-isobaric semi-grand ensemble consisted of par-

ticle displacements, isotropic volume changes, and identity

change moves. The Monte Carlo simulations of the CsCl

phase consisted of particle displacements, volume moves, and

swap moves between unlike particle. Each of these simula-

tions consisted of 50 000 equilibration cycles and 200 000

production cycles. Unlike the earlier work, the addition of

particle swap moves introduces an extra rigor where imper-

fections in substitutional order of the CsCl phase are allowed.

These imperfections become signiﬁcant at higher tempera-

tures and contribute to the free energy of the CsCl phase. The

free energies and the chemical potentials at the reference state

are computed using the method of Hamiltonian integration

17

for the ﬂuid phase and Frenkel-Ladd technique

18, 19

for the

solid phases. The reference states were T

∗

= 1.0, x

A

= 1.0,

and packing fraction η = 0.458 for the ﬂuid phase; and

T

∗

= 1.0, x

A

= 1.0, and η = 0.539 for the FCC phase. The

value of the spring constant used in the Frenkel-Ladd simu-

lations was equal to 650. Since we allowed for particle swap

moves in the CsCl phase, the Frenkel-Ladd technique was car-

ried out at a lower temperature of T

∗

= 0.5 and η = 0.539

where the acceptance of the particle swap moves was zero.

The value of the spring constant used in the Frenkel-Ladd

simulations for the CsCl phase was equal to 650.

The coexistence pressures, P

∗

(=Pσ

3

/), for the ﬂuid-

FCCand ﬂuid-CsCl equilibriumwere computed to be equal to

11.32 ± 0.025 and 11.74 ± 0.03, respectively. As mentioned

earlier, these serve as the starting point for the Gibbs-Duhem

integration. The triple point is computed by integrating

Eqs. (7) and (8) at constant T

∗

= 1.0 and α = −1. All

8

9

10

11

12

13

14

15

16

0 5 10 15 20 25 30 35

κσ

Pσ

3

k

B

T

fluid-FCC

fluid-CsCl

FIG. 1. Variation of coexistence pressure at the ﬂuid-FCC and ﬂuid-CsCl

phase equilibrium at constant T

∗

= 1.0 and α = −1.

the Gibbs-Duhem differential equations in this study were

numerically integrated using the fourth-order Runge-Kutta

method. The result is shown in Fig. 1. The intersection of the

two curves shown in Fig. 1 is the triple point corresponding

to the three phase equilibrium between the ﬂuid-phase with

x

A

= 0.5, the CsCl phase and FCC phase at T

∗

= 1.0 and α

= −1. The values of P

∗

and κσ at this triple point are equal

to 12.02 ± 0.055 and 19.75 ± 0.517, respectively. The de-

termination of the triple point allows us to study its variation

across T

∗

, κσ, and α using Eqs. (9)–(12). The variation of

the triple point at constant T

∗

= 1.0 along the α–κσ plane is

shown in Fig. 2. This ﬁgure provides a map of inter-particle

interactions depicting regions which favor the formation of a

particular solid phase. In Fig. 2, the region below the curve

represents the conditions (in terms of α and κσ) at which an

equimolar ﬂuid phase upon phase transition forms the CsCl

phase while that above the curve represents conditions for the

formation of the FCC phase. The curve shows a maximum

at κσ = 6.95 where the value of α is equal to −0.71. This

further validates the conclusion in Ref. 14 that there exists an

optimum value of screening, κσ, which favors the formation

-1

-0.9

-0.8

-0.7

-0.6

-0.5

-0.4

3 6 9 12 15 18 21

α

κσ

CsCl

FCC

FIG. 2. The ﬂuid-FCC-CsCl triple point line on the α–κσ plane at T

∗

= 1.0

demarcating regions where an equimolar ﬂuid will undergo phase transition

to CsCl phase or FCC phase.

174504-5 G. Pavaskar and S. N. Punnathanam J. Chem. Phys. 138, 174504 (2013)

-1

-0.8

-0.6

-0.4

-0.2

0

3 6 9 12 15 18 21 24 27 30

α

κσ

T

*

= 1.3

T

*

= 1.2

T

*

= 1.1

T

*

= 1.0

T

*

= 0.9

T

*

= 0.8

T

*

= 0.7

T

*

= 0.6

T

*

= 0.5

FIG. 3. The ﬂuid-FCC-CsCl triple point line on the α–κσ plane at various

values of T

∗

. The cross symbol depicts the conditions under which the CsCl

superlattice was synthesized in Ref. 7.

of the substitutionally ordered CsCl phase. The existence of

this optimum is explained as follows. Since CsCl is substitu-

tionally ordered, it has a lower energy and entropy compared

to the FCC phase. When competing with the FCC phase, it is

favored if its energy is sufﬁciently lower than the FCC phase.

At high values of κσ, the energy of interaction among the par-

ticles is reduced. This favors the formation of the FCC phase.

The gain in the energy due to substitutional order of CsCl also

decreases at lower than optimum values of κσ but for differ-

ent reasons. When the extent of charge screening decreases

the range of interaction increases. So in the CsCl phase, each

particle interacts not only with its oppositely charged nearest

neighbors but also similarly charged next nearest neighbors,

lowering the gain in the energy of the CsCl phase compared

to the FCC phase. This again favors the formation of the FCC

phase. During these investigations, the interaction energies in

the Monte Carlo simulations were computed using a spherical

cutoff equal to 2.5 σ followed by incorporation of long range

interactions assuming uniform concentrations. Since this ap-

proximation fails at low values of κσ, the lower limit of κσ

was kept equal to 3.0.

We also computed the triple points at various tempera-

tures. Again these were computed by integrating Eqs. (9)–

(12). The computed triple points are shown in Fig. 3. The

lowest temperature explored was T

∗

= 0.5. Simulations of

the ﬂuid phase at T

∗

< 0.5 are difﬁcult since the oppositely

charged particles stick to each other and form a gel-like net-

work. The maximum temperature that favors the formation

of the CsCl phase was computed to be T

∗

= 1.37. Figure 3

shows that the optimum value of κσ that favors the forma-

tion of the CsCl phase is nearly invariant with a value close to

7.0 (see Fig. 4). Figure 5 shows the minimum value of α that

is necessary for the formation of CsCl phase. Figure 3 thus

provides us with a map of inter-particle interactions showing

regions that favor the formation of various solid phases. We

can compare this map with the conditions under which the

CsCl superlattice was synthesized as reported in Ref. 7. In

that study, the values of α and κσ were equal to −0.682 and

7.263, respectively. The contact energy of oppositely charged

particles as computed using Eq. (2) of Ref. 7 was equal to

0

1

2

3

4

5

6

7

8

9

10

0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3

κ

σ

T

*

FIG. 4. The optimum value of κσ at various temperatures that favor the for-

mation of the CsCl phase. The line is a guide to the eye.

−1.86 k

B

T. The contact energy as obtained from Eq. (1) is

−0.682. (This value is obtained by setting Z

A

= 1.0 and

Z

B

= α.) Equating the two values of the contact energy we

obtain T

∗

= k

B

T/ = 0.367. This condition under which the

CsCl superlattice was synthesized is depicted in Fig. 3 by the

cross symbol. For T

∗

= 0.367, this point lies in the region fa-

voring the formation of CsCl phase from an equimolar binary

mixture of oppositely charged particles indicating consistency

of our simulation results with the experimental data of Leu-

nissen et al.

7

Interestingly, the value of κσ is close to the op-

timum value as shown in Fig. 4. The variation of pressure and

packing fraction of the ﬂuid phase at coexistence along the

triple point lines are shown in Figs. 6 and 7, respectively. In-

terestingly, the ﬂuid phase packing fraction is nearly constant

along the triple point lines.

As mentioned earlier, the simulations of CsCl phase in-

cluded particle swap moves, which create imperfections in the

substitutional order of the particles. These imperfections were

quantiﬁed using an order parameter, θ, which is deﬁned as the

average mole fraction of particle B among the eight nearest

neighbors of A particles. For a perfect substitutional order,

-1

-0.9

-0.8

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0

0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3

α

T

*

FIG. 5. The minimum value of α needed at various values of T

∗

for the

formation of the CsCl phase from an equimolar ﬂuid phase. The line is a

guide to the eye.

174504-6 G. Pavaskar and S. N. Punnathanam J. Chem. Phys. 138, 174504 (2013)

10

-1

10

0

10

1

10

2

10

3

10

4

3 6 9 12 15 18 21 24 27 30

κσ

Pσ

3

k

B

T

T

*

= 1.3

T

*

= 1.2

T

*

= 1.1

T

*

= 1.0

T

*

= 0.9

T

*

= 0.8

T

*

= 0.7

T

*

= 0.6

T

*

= 0.5

FIG. 6. Variation of pressure along ﬂuid-FCC-CsCl triple point line for var-

ious values of T

∗

.

value of θ is equal to one and for complete random mixing

the value of θ will be equal to 0.5. The value of θ will depend

on temperature, packing fraction, κσ, and α. Figure 8 shows

the values of θ at various points along the three-phase equilib-

rium lines. Remarkably, the value of θ is nearly independent

of T

∗

. These values can be considered as the lower limit of θ

for the CsCl phase. During synthesis of CsCl superlattice via

self-assembly, the conditions will usually be far away from

the three-phase equilibrium line. Under these conditions, the

average potential energy due to attraction between oppositely

charged particles will be higher and consequently one should

expect a higher value for θ.

Finally we would like to comment on the nature of the

triple points computed. In this study, the triple points repre-

sent coexistence between the ﬂuid phase at equimolar com-

position, the FCC phase, and CsCl phase. At this triple point,

the composition of the FCC phase is not equimolar in gen-

eral. The FCC phase is equimolar only when α = −1, i.e.,

when the system is symmetric. The variation of the composi-

tion of the FCC phase is given in Fig. 9. We observe that for

asymmetric mixtures, i.e., when α > −1, the FCC phase is

richer in component B, i.e., x

A

< 0.5. This can be explained

0.2

0.3

0.4

0.5

0.6

0.7

0.8

3 6 9 12 15 18 21 24 27 30

η

κσ

T

*

= 1.3

T

*

= 1.2

T

*

= 1.1

T

*

= 1.0

T

*

= 0.9

T

*

= 0.8

T

*

= 0.7

T

*

= 0.6

T

*

= 0.5

FIG. 7. Variation of ﬂuid phase packing fraction along ﬂuid-FCC-CsCl triple

point line for various values of T

∗

.

0.5

0.6

0.7

0.8

0.9

1

3 6 9 12 15 18 21 24 27 30

θ

κσ

T

*

= 1.3

T

*

= 1.2

T

*

= 1.1

T

*

= 1.0

T

*

= 0.9

T

*

= 0.8

T

*

= 0.7

T

*

= 0.6

T

*

= 0.5

FIG. 8. Variation of order parameter, θ, quantifying imperfections in substi-

tutional ordering in the CsCl phase at various points along the three-phase

equilibrium lines.

through Fig. 10 which is a schematic of a P–x phase diagram

at the triple point. The schematic has been constructed based

on the prior studies of such systems.

14

The P–x phase diagram

shows two triple points. One of the triple points lie when the

ﬂuid composition x

A

= 0.5. Figure 3 shows the locus of these

triple points on the α–κσ plane. The coexisting FCC phase

at this triple point is richer in component B. The other triple

point exists for a ﬂuid composition x

A

>0.5. Fluids with com-

positions lying between these two triple points are in equilib-

rium with the CsCl phase. If we further increase the charge ra-

tio, α, keeping the value of κσ constant, an equimolar binary

Yukawa ﬂuid mixture can only form the FCC phase. How-

ever, the CsCl phase can still be formed if the ﬂuid is richer in

component A. While constructing the schematic, it is assumed

that an azeotrope exists between the ﬂuid and the FCC phase.

Further it is also assumed that the FCC phase at the second

triple point is also richer in component B. These assumptions

may not hold for all the triple points shown in Fig. 3 but other

observations regarding the structure of the P–x phase diagram

will still hold.

0.4

0.42

0.44

0.46

0.48

0.5

0.52

0.54

0.56

0.58

0.6

3 6 9 12 15 18 21 24 27 30

x

A

κσ

T

*

= 1.3

T

*

= 1.2

T

*

= 1.1

T

*

= 1.0

T

*

= 0.9

T

*

= 0.8

T

*

= 0.7

T

*

= 0.6

T

*

= 0.5

FIG. 9. Variation of mole fraction in the FCC phase along ﬂuid-FCC-CsCl

triple point line for various values of T

∗

.

174504-7 G. Pavaskar and S. N. Punnathanam J. Chem. Phys. 138, 174504 (2013)

FIG. 10. Schematic of a P–x phase diagram of a binary mixture of oppo-

sitely charged hard core Yukawa particles with a triple point at the ﬂuid com-

position of x

A

= 0.5.

V. CONCLUSIONS

In this study, we explored the formation of substitution-

ally ordered crystalline structures from a binary mixture of

equal sized but oppositely charged colloidal particles. Using

the method of Gibbs-Duhem integration, the phase equilib-

ria were computed at various temperatures, charge ratio, and

charge screening. Under the conditions studied, the only sub-

stitutionally ordered crystalline structure that is stable is the

one analogous to CsCl. The study conﬁrmed the observation

from an earlier work about the existence on an optimum range

of charge screening that favors the formation of the CsCl

phase. Through this study, we are able to generate a map of

interactions depicting regions that favor formation of various

solid phases by phase transition from a ﬂuid phase. These re-

sults are also consistent with previously published data

7

on

synthesis of superlattices from oppositely charged colloidal

particles. Although the inter-particle interactions were mod-

eled using the hard core Yukawa potential, this method can

be readily applied to colloidal systems with different types

of interactions. The maps of interactions generated from such

studies provide a useful guide for synthesis of crystalline ag-

gregates of colloidal particles.

ACKNOWLEDGMENTS

The ﬁnancial support for this work has been provided

by grants from the Department of Science and Technology,

Government of India.

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