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Z
i
Z
j
e
(
r
ij
)
r
ij
/
if r
ij
if r
ij
<
, (1)
where u is the inter-particle potential energy, r
ij
is the distance
between particles i and j, and 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, , that is
dened to be the ratio of the charge on particle B to that of
particle A, i.e., = 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/), , and , where
T is the temperature and k
B
is the Boltzmann constant. In
Ref. 14, it was observed that for T
= 1.0 and = 1,
the equimolar uid crystallized into the CsCl phase when
= 6.0 and into FCC phase when . Hence at
a denite value of > 6.0, all the three phases will be in
equilibrium. When is larger than this particular value, the
uid is in equilibrium with FCC phase and at lower values the
uid is in equilibrium with the CsCl phase. The location of
the triple point depends on the value of T
, , and .
Our aim is to trace the locus of triple points as a function
of T
A
T
_
P,,,x
A
dT +
_
A
P
_
T,,,x
A
dP
+
_
_
T,P,,x
A
d
+
_
_
T,P,,x
A
d +
_
A
x
A
_
T,P,,
dx
A
,
(2)
d
B
=
_
B
T
_
P,,,x
A
dT +
_
B
P
_
T,,,x
A
dP
+
_
_
T,P,,x
A
d
+
_
_
T,P,,x
A
d +
_
B
x
A
_
T,P,,
dx
A
,
(3)
where =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
A
= G+(1 x
A
)
_
G
x
A
_
T,P,,
,
B
= Gx
A
_
G
x
A
_
T,P,,
.
Substitution of these identities in the Eqs. (2) and (3) fol-
lowed by application of thermodynamic relations results in
the following equations:
d
A
= H
A
d +V
A
dP +W
A
d +Y
A
d
+(1 x
A
)
_
x
A
_
T,P,,
dx
A
, (4)
174504-3 G. Pavaskar and S. N. Punnathanam J. Chem. Phys. 138, 174504 (2013)
d
B
= H
B
d +V
B
dP +W
B
d +Y
B
d
x
A
_
x
A
_
T,P,,
dx
A
, (5)
where H is the molar enthalpy, V is the molar volume,
W = (G/)
T,P,,x
A
, Y = (G/)
T,P,,x
A
, and
=
A
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
dG = Hd +VdP +Wd +Yd. (6)
B. Two-phase equilibrium
The criteria for phase equilibriumbetween the uid phase
and FCC phase are
(l)
A
=
(s)
A
,
(l)
B
=
(s)
B
,
where the superscripts l and s represent the uid phase and
the FCC phase, respectively. If the uid composition is kept
xed then, upon substitution from Eqs. (4) and (5) followed
by elimination of x
s
A
we have
H
(ls)
d +V
(ls)
dP +W
(ls)
d +Y
(ls)
d = 0,
(7)
where
H
(ls)
= 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
(ls)
= 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
(ls)
= 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
(ls)
= 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 uid phase and the
CsCl phase is given as
G
(c)
=
(l)
A
+
(l)
B
2
,
where the superscript c represents the CsCl phase. Again
keeping the uid composition xed, upon substitution from
Eqs. (4)(6) we have
H
(lc)
d +V
(lc)
dP +W
(lc)
d +Y
(lc)
d = 0,
(8)
where
H
(lc)
= (H
(l)
H
(c)
),
V
(lc)
= (V
(l)
V
(c)
),
W
(lc)
= (W
(l)
W
(c)
),
Y
(lc)
= (Y
(l)
Y
(c)
).
C. Three-phase equilibrium
Equations (7) and (8) give the loci of points correspond-
ing to the uid-FCC phase equilibrium and uid-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 uid, 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
(ls)
H
(lc)
V
(lc)
H
(ls)
)dP
+(W
(ls)
H
(lc)
W
(lc)
H
(ls)
)d
+(Y
(ls)
H
(lc)
Y
(lc)
H
(ls)
)d = 0. (9)
Eliminating P from Eqs. (7) and (8) we get
(H
(ls)
V
(lc)
H
(lc)
V
(ls)
)d
+(W
(ls)
V
(lc)
W
(lc)
V
(ls)
)d
+(Y
(ls)
V
(lc)
Y
(lc)
V
(ls)
)d = 0. (10)
Eliminating from Eqs. (7) and (8) we get
(H
(ls)
W
(lc)
H
(lc)
W
(ls)
)d
+(V
(ls)
W
(lc)
V
(lc)
W
(ls)
)dP
+(Y
(ls)
W
(lc)
Y
(lc)
W
(ls)
)d = 0. (11)
Eliminating from Eqs. (7) and (8) we get
(H
(ls)
Y
(lc)
H
(lc)
Y
(ls)
)d
+(V
(ls)
Y
(lc)
V
(lc)
Y
(ls)
)dP
+(W
(ls)
Y
(lc)
W
(lc)
Y
(ls)
)d = 0. (12)
D. Computation of properties
The equations derived for the Gibbs-Duhem integration
are rst order differential equations. The quantities on the
right hand side of the differential equation are computed us-
ing simulations. These simulations for the uid phase and
substitutionally disordered FCC phase are carried out in the
isothermal-isobaric semi-grand ensemble (constant N, P, T,
) 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
_
,
Y =
_
U
_
,
where U is the potential energy of the system. In addition,
the computation of the partial molar properties in the uid
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 uctuation 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 uid-
FCC and uid-CsCl coexistence point. The composition of
uid phase is x
A
= 0.5. The equilibrium is computed for con-
ditions T
= 1.0, x
A
= 1.0,
and packing fraction = 0.458 for the uid phase; and
T
= 1.0, x
A
= 1.0, and = 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
(=P
3
/), for the uid-
FCCand uid-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
P
3
k
B
T
fluid-FCC
fluid-CsCl
FIG. 1. Variation of coexistence pressure at the uid-FCC and uid-CsCl
phase equilibrium at constant T
= 1.0 and = 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 uid-phase with
x
A
= 0.5, the CsCl phase and FCC phase at T
= 1.0 and
= 1. The values of P
CsCl
FCC
FIG. 2. The uid-FCC-CsCl triple point line on the plane at T
= 1.0
demarcating regions where an equimolar uid 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
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 uid-FCC-CsCl triple point line on the 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 sufciently lower than the FCC phase.
At high values of , 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 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 followed by incorporation of long range
interactions assuming uniform concentrations. Since this ap-
proximation fails at low values of , the lower limit of
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 uid phase at T
= 1.37. Figure 3
shows that the optimum value of 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 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 and 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
T
*
FIG. 4. The optimum value of 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
= .) 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
T
*
FIG. 5. The minimum value of needed at various values of T
for the
formation of the CsCl phase from an equimolar uid 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
P
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 uid-FCC-CsCl triple point line for var-
ious values of T
.
value of is equal to one and for complete random mixing
the value of will be equal to 0.5. The value of will depend
on temperature, packing fraction, , and . Figure 8 shows
the values of at various points along the three-phase equilib-
rium lines. Remarkably, the value of is nearly independent
of 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. 7. Variation of uid phase packing fraction along uid-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
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, , 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 Px phase diagram
at the triple point. The schematic has been constructed based
on the prior studies of such systems.
14
The Px phase diagram
shows two triple points. One of the triple points lie when the
uid composition x
A
= 0.5. Figure 3 shows the locus of these
triple points on the plane. The coexisting FCC phase
at this triple point is richer in component B. The other triple
point exists for a uid 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, , keeping the value of constant, an equimolar binary
Yukawa uid mixture can only form the FCC phase. How-
ever, the CsCl phase can still be formed if the uid is richer in
component A. While constructing the schematic, it is assumed
that an azeotrope exists between the uid 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 Px 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
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 uid-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 Px phase diagram of a binary mixture of oppo-
sitely charged hard core Yukawa particles with a triple point at the uid 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 conrmed 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 uid 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 nancial support for this work has been provided
by grants from the Department of Science and Technology,
Government of India.
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