Crystal nucleation in binary hard sphere mixtures: A Monte Carlo simulation study

S. Punnathanam and P. A. Monson

Citation: The Journal of Chemical Physics 125, 024508 (2006); doi: 10.1063/1.2208998
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 THE JOURNAL OF CHEMICAL PHYSICS 125, 024508 2006

Crystal nucleation in binary hard sphere mixtures: A Monte Carlo

simulation study
S. Punnathanam and P. A. Monsona
Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003
Received 11 January 2006; accepted 8 May 2006; published online 14 July 2006

We present calculations of the nucleation barrier during crystallization in binary hard sphere
mixtures under moderate degrees of supercooling using Monte Carlo simulations in the
isothermal-isobaric semigrand ensemble in conjunction with an umbrella sampling technique. We
study both additive and negatively nonadditive binary hard sphere systems. The solid-fluid phase
diagrams of such systems show a rich variety of behavior, ranging from simple spindle shapes to the
appearance of azeotropes and eutectics to the appearance of substitutionally ordered solid phase
compounds. We investigate the effect of these types of phase behavior upon the nucleation barrier
and the structure of the critical nucleus. We find that the underlying phase diagram has a significant
effect on the mechanism of crystal nucleation. Our calculations indicate that fractionation of the
species upon crystallization increases the difficulty of crystallization of fluid mixtures and in the
absence of fractionation azeotropic conditions the nucleation barrier is comparable to pure fluids.
We also calculate the barrier to nucleation of a substitutionally ordered compound solid. In such
systems, which also show solid-solid phase separation, we find that the phase that nucleates is the
one whose equilibrium composition is closer to the composition of the fluid phase.
2006 American Institute of Physics. DOI: 10.1063/1.2208998

I. INTRODUCTION tem as a function of the nucleus size shows a maximum. The

It is well known that fluid mixtures are generally harder
to crystallize compared to pure fluids.15 In addition, the
solid-fluid phase behavior of mixtures shows a rich variety
compared to that of pure fluids. The phase diagrams of even
binary mixtures613 vary from simple spindle shaped struc-
ture to complex ones showing azeotropes, eutectic points,
peritectic points, compound solid formation, etc. Although
there have been some studies3,4,1417 of crystal nucleation in
fluid mixtures using molecular simulations, the influence of
these phenomena on the dynamics of crystal formation is
largely unknown and it is of fundamental interest to under-
stand the mechanism of crystal formation in such systems.
The purpose of this paper is to study the mechanism of crys-
tal formation using molecular simulations in model systems
that exhibit the above phenomena.
The primary mechanism of crystal formation from a su-
percooled fluid is via nucleation.18,19 A qualitative under-
standing of nucleation is provided by the classical nucleation
theory CNT developed in the works of Volmer,20 Becker,21
Zeldovich,22 Frenkel,23 and others. According to the theory,
the process of formation of a nucleus requires work to form
the interface between the crystal and the fluid. This is offset
by the reduction in the free energy upon formation of the
solid phase. The former is proportional to the surface area of
the nucleus and is positive while the latter is proportional to
the volume of the nucleus and is negative. For small sizes the
surface term dominates while for larger sizes the volume
term dominates. As a result the total free energy of the sys-
a
Electronic mail: monson@ecs.umass.edu
nucleus for which this maximum occurs is called the critical
nucleus and the difference between this maximum of the free
energy and that of the metastable fluid is the work of forma-
tion of the critical nucleus G*. Only those crystal nuclei
larger than the critical nucleus grow further in size to form
the new solid phase. Nucleation, hence, is an activated pro-
cess and its rate depends on G*,
j = exp G*/kBT, 1
where j is the rate of formation of the critical nuclei per unit
volume per unit time, kB is Boltzmann constant, T is the
absolute temperature, and is the kinetic factor which gives
the rate of growth of the critical nucleus. Thus the rate of
nucleation depends upon the thermodynamics properties of
the critical nucleus. Although crystal nucleation has been
widely studied, our understanding of its mechanism remains
incomplete.19 This is mainly because direct experimental ob-
servation of the critical nucleus is very difficult19 since i it
is microscopic in size consisting of few hundreds of par-
ticles, ii its formation is very rare typically
101 106 nuclei cm3 s, and iii its lifetime is very short it
either rapidly grows to form a solid phase or melts back into
the fluid. However, recent experiments on colloidal
systems24,25 show considerable promise. Colloidal systems
behave similar to atomistic systems and can form
crystals.19,26 However, due to their much larger size, the dy-
namics of colloidal crystallization is much slower giving an
opportunity to observe the critical nucleus directly using
techniques such as confocal microscopy or laser light scat-
tering and obtain information about its composition and
structure.19,25,27

0021-9606/2006/1252/024508/11/$23.00 125, 024508-1 2006 American Institute of Physics

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 024508-2 S. Punnathanam and P. A. Monson J. Chem. Phys. 125, 024508 2006

CNT models the critical nucleus as a spherical solid
cluster suspended in the metastable fluid and its thermody-
namic properties are approximated by the corresponding val-
ues for a bulk solid phase. The value for the interfacial ten-
sion between the nucleus and the surrounding metastable
fluid is approximated by the planar surface tension between
the two phases at coexistence. For a binary system consisting
of species A and B, G* can be obtained by solving the
following sets of equations:28
AlP = AsP + P* PvAs , 2 mixtures. Hard sphere systems were studied because they are
BlP = BsP + P* PvBs , 3 transition48 and their thermodynamic properties are well
2 achieved by isothermally compressing the system above its
r* = , 4
P P
*
4 *2
G* = r ,
3 thus compression of a hard sphere system may be interpreted
where i is the chemical potential, vi is the partial molar
volume of component i, P* is the pressure inside the nucleus,
P is the pressure of the fluid, and r* is the radius of the
spherical nucleus. The superscripts l and s denote the fluid
and solid phases, respectively. The main criticisms of CNT
are the use of the properties of the macroscopic phases to
model the critical nucleus and the use of the planar surface
tension to obtain the surface energy of the nucleus. These
assumptions get increasingly tenuous at higher degrees of
supercooling when the critical nucleus is microscopic in size
leading to a breakdown in the predictions of CNT. However,
CNT remains an important framework and a significant
amount of research,29 as well as our general understanding of
the mechanism, is still grounded in the description provided
by CNT and captured in Eq. 1.
Due to the microscopic nature of the critical nucleus,
molecular simulations are an attractive tool for studying
crystal nucleation. As described in a recent review by Auer
and Frenkel,30 molecular simulation studies of crystal nucle-
ation using direct molecular dynamics MD simulations
have many difficulties because nucleation is a rare event and
under experimental conditions they occur at time scales that
are more than 20 orders of magnitude larger than those in-
volved with molecular motion. Hence crystallization simula-
tions were performed at very large supercoolings3,3144 where
the nucleation rates are higher. But as explained by Auer and
Frenkel,30 the mechanism may be different than in experi-
ments due to the simultaneous formation of multiple inter-
acting crystal nuclei. To overcome this, they have suggested
an indirect approach4,27,4547 which takes advantage of the
form of the nucleation rate given by Eq. 1. Instead of di-
rectly calculating the nucleation rate j, one instead calculates
G* and separately and substitutes it back into Eq. 1 to
obtain j. In this paper our focus is on the calculation of G*
for binary mixtures. The basic idea is to use umbrella sam-
pling combined with replica switch methods to sample the
to search out more efficiently the regions of phase space
associated with crystal nuclei without the attendant difficul-
ties of molecular dynamics. They applied their technique to
study crystal nucleation in simple atomic systems consisting
of Lennard-Jones46 or hard sphere particles47 and showed
that it was possible to obtain the free energy barrier to nucle-
ation as well as size and structure of the critical nucleus for
supercoolings as low as 20%.
In this work, we apply the methods of Frenkel and co-
workers to study crystal nucleation to binary hard sphere
the most simple models that exhibit solid-fluid phase
known. In the case of hard sphere systems, crystallization is
freezing pressure. However, we will be using the term super-
cooling to denote compression above the freezing pressure
since the dimensionless hard sphere pressure may be inter-
5 preted as the reciprocal of a dimensionless temperature and
as an isobaric cooling process.49 The phase diagrams for bi-
nary hard sphere systems have been computed
previously713,50 and they are a good model for studying the
underlying physics involved in solid-fluid phase equilibria of
binary mixtures. Based on a survey of the data for phase
diagrams for binary organic mixtures Matsuoka6 were able to
classify them into six different types. Binary hard sphere
systems exhibit five of those six types of phase diagrams,
illustrating the importance of packing and molecular size dif-
ferences upon solid phase stability and crystal structure. The
only phase diagrams that binary hard sphere mixtures do not
exhibit are those that show congruent melting of compound
solids. However, as we shall see later, congruent melting can
be obtained if one introduces nonadditivity in the hard sphere
diameter for the interaction between the unlike components.
This idea comes from studies of solid-fluid phase diagrams
of symmetric nonadditive Lennard-Jones 12-6 mixtures by
Vlot et al.51 who showed that such systems can exhibit con-
gruent melting.
The remainder of the paper is organized as follows. In
Sec. II we describe the methods used for simulation of crys-
tal nucleation in binary hard sphere systems. The results
from our simulation study for crystal nucleation in binary
mixtures are presented in Sec. III. Finally, a summary of our
results and conclusions is presented in Sec. IV.
II. MODELS AND SIMULATION DETAILS
A. Models
The model systems used in our study are binary hard
sphere mixtures comprised of two species denoted as A and
B. The interaction potential uijr between two particles be-
longing to species i and j is given by
uijr = if r ij
0 if r ij ,
6

fluctuations that give rise to crystal nuclei and to calculate where r is the intermolecular distance and ij is the distance
the free energy of formation of these nuclei as a function of of closest approach between two particles belonging to spe-
their size. These biased sampling methods make it possible cies i and j. According to this notation, AA is the hard
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 024508-3 Crystal nucleation in mixtures
sphere diameter of species A and BB is the hard sphere
diameter of species B. In this paper, we study both additive
and nonadditive hard sphere systems. By convention, the
larger species is denoted by A and the smaller species by B.
The ratio of the diameters is given by = BB / AA. The hard
sphere interaction distance between species A and B is de-
noted by
AB = 21 AA + BB1 + , 7 calculate Prn via Monte Carlo simulations. Once Gn is
where = 0 for the case of additive hard spheres and 0 the maximum in the plot of Gn versus n. The location of
for nonadditive hard spheres.
B. Calculation of phase diagram
Before one proceeds with study of crystal nucleation, it
is essential to calculate the solid-fluid phase diagram of the
system. The phase diagrams for additive hard sphere systems
studied here have been previously calculated by various
authors.1113,50 We have recalculated some of these phase
diagrams and also the phase diagram for a nonadditive sym-
metric hard sphere mixture with = 0.1. In the case of ad-
ditive hard sphere systems, we use the equation of state of
Mansoori et al.52 for fluid mixtures. The equation of state for
fluid mixtures of nonadditive hard spheres and substitution-
ally disordered solid mixtures is calculated by isothermal-
isobaric semigrand ensemble see Sec. II C 2. These simu-
lations give us the composition of the mixture as a function
of the pressure and the chemical potential difference. Com-
bining these calculations with the equation of state for pure
hard spheres53,54 gives us the chemical potentials of both
species at various compositions and pressures. For the case
of substitutionally ordered solids, we also need their Gibbs
free energies. These are calculated using the method of Fren-
kel and Ladd.55
The calculation of the solid-fluid equilibria between fluid
mixtures and substitutionally disordered solid solutions is
done by equating the pressures and the chemical potentials of
each species between the two phases. For the case of the
equilibrium between the fluid mixture and the substitution-
ally ordered solid compound, the equilibrium conditions are
modified by the stoichiometric constraints.8 In general for a
compound solid AmBn, where the two species are present in
the ratio m : n, we have
m + nGAmBn = mAl + nBl ,
where GAmBn is the Gibbs free energy of the compound solid
and Al and Bl are the chemical potentials of species A and B
in the fluid, respectively. At equilibrium the two phases sat-
isfy Eq. 8 at the same pressure.
C. Simulation of nucleation
This paper focuses on the calculation of G*. We closely
follow the method developed by Frenkel and
co-workers4,27,4547 for calculating G*. For complete details
of the method, the reader should consult Ref. 27. The value
of G* can be obtained from the probability of formation of
the critical nucleus. Let Prn be the probability of observing
at least one nucleus containing n particles. When the value of
Prn is very low, then Nn = Prn, where Nn is the number of
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J. Chem. Phys. 125, 024508 2006
nuclei containing n particles. Nn is related to Gn, the
work of formation of a nucleus containing n particles by27
Nn
N
= exp
Gn
k BT
, 9
where kB is Boltzmanns constant, T is the absolute tempera-
ture, and N is the total number of particles in the system. We
obtained using Eq. 9 for a range of values of n, we locate
the maximum determines the critical nucleus and the height
of the maximum gives G*. Although the method described
there pertains to simulation of crystal nucleation in single
component systems, with suitable modifications we can ex-
tend it to study crystal nucleation in binary systems.
1. Identification of crystal nuclei
As explained in Ref. 27, the simulation relies on the
ability to identify a crystalline nucleus inside a metastable
fluid. The method is based on the local bond analysis of
Steinhardt et al.56 We define for every particle i, a
2l + 1-dimensional complex vector qli, with components
Nbi
1
qlmi =
Nbi
j=1
Y lmrij, 10
where Nb is the number of neighboring particles and Y lm are
the spherical harmonics for the normalized direction vector
rij, between particles i and j. Neighbors are defined as those
particles which lie within a given cutoff radius rc. For the
calculations in this paper, we use a value of rc = 1.3AA.
Similar to calculations in Ref. 27, we use a value of l = 6. In
a crystalline environment, these vectors are aligned with
each other but in a fluidlike environment they are randomly
oriented. To obtain a measure of the alignment, we calculate
the correlation between the vectors q6 of neighboring par-
ticles i and j,
6
q6i . q6j = q6miq6m
m=6
*
j, 11
where
q6mi
8 q6mi = . 12
q6mi
The asterisk in Eq. 11 denotes the complex conjugate.
Equation 11 is a dot product between two normalized vec-
tors and gives the cosine of the angle between them. A value
of 0.7 is chosen to determine whether the two neighboring
particles are aligned or not. We identify those particles as
solid if the number of aligned neighbors are greater than 5
and as fluid otherwise. Once all the solid particles are iden-
tified, we then determine the particles to belong to the same
cluster as they are separated by a distance less than rc.
We can also analyze the structure of the crystal nuclei
formed during simulations using these order parameters. The
vectors qli depend on the orientation of the coordinate sys-
tem used. From these vectors one can obtain local second
order invariants defined as
 024508-4 S. Punnathanam and P. A. Monson
qli = 4
l
qlmi2
2l + 1 m=l
1/2
. 13
In order to determine the structure of the crystal nucleus, we
first calculate the distribution of qli for the particles of the
nucleus. Comparison of the distribution with that of bulk
solid phases will help in identifying the structure of the
nucleus.
2. Isothermal-isobaric semigrand ensemble
During the simulations, the crystal nucleus that is
formed has in general a concentration that is different from
that of the fluid. Hence, the simulations were performed in
the isothermal-isobaric semigrand ensemble. In this en-
semble we fix the temperature T, pressure P, total number of
particles N, and the chemical potential difference be-
tween the two species. This allowed us to maintain the fluid
at the same degree of supercooling even after the crystal
nucleus is formed. The simulation box is cubic in shape.
During simulations one of particles is kept on the surface of
the simulation box and its movement is restricted to that one
face of the cube. This particle is the shell particle and it
defines the volume of the system.57,58 The partition function
of this semigrand ensemble for a binary mixture is given as
1
Y=
B3NN! identities
NA
dV dr2 drNeU+PV , 14
where U is the potential energy of the system of N particles
at positions r1 rN, NA is the number of particles of species
A, = 1 / kBT, V is the volume of the system,
= eB3 / A3 , = A B, i is the chemical potential of
species i, and i is its de Broglie wavelength. The summa-
tion is done for every particle where its identity changes
from one component to another.59 During simulations, we
make particle displacements and volume changes. In addi-
tion, we also switch the identity of each particle between the
two species, i.e., we change the diameter of the particle. The
acceptance or rejection of these moves is governed by the
chemical potential difference. Typically during simulations,
samples are made after every Monte Carlo move. In the case
of the cluster size distribution, however, the calculations in-
volved during the sampling are computationally expensive
and the samples are strongly correlated. Hence cluster size
distributions are calculated after a fixed number of Monte
Carlo moves called a trajectory. For all the calculations, the
averages were collected over 100 000 trajectories following
an equilibration period of 50 000 trajectories. Repeated
simulations indicate that the uncertainties in the values of the
calculated free energies of formation of the nuclei are kBT.
3. Umbrella sampling with parallel tempering
In our simulations, we are interested in the properties of
the critical cluster. At the degrees of supercooling that we
study, the free energies of formation of these clusters are
higher than 15kBT. Hence their occurrence in a normal unbi-
ased Monte Carlo simulation is very rare. In order to simu-
late these large clusters, we resort to umbrella sampling
technique of Torrie and Valleau.60 For details of its imple-
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J. Chem. Phys. 125, 024508 2006
mentation, the reader is once again referred to Auer and
Frenkel.27 The biasing potential is a harmonic function
given by
rN = 21 knrN n0, 15
where nrN is the size of the largest cluster and k and n0 are
the parameters of the biasing potential. Application of this
biasing potential gives us cluster size distributions centered
around n0 with a width that depends on k. We use a value of
k = 0.15 for all the calculations shown in this paper. The free
energy profile is obtained by running simulations with differ-
ent values of n0, such that one obtains cluster size distribu-
tions for a set of overlapping windows. During simulations,
stacking rearrangements in the cluster are very slow. In order
to overcome the barriers towards stacking arrangements, all
the windows are simulated in parallel using the parallel tem-
pering technique of Geyer and Thompson.61 Again our
implementation follows very closely with that given in
Ref. 27.
4. Augmented semigrand ensemble
The above method works well when is close to unity.
However, when becomes smaller, it becomes harder to
change the diameter of a particle and the efficiency of par-
ticle identity changes becomes very poor. As a result it will
take much longer for the composition of the mixture to reach
the equilibrium value. One way to overcome this problem is
to change the diameter of the particles gradually in several
stages. In the literature, many methods6272 have been pro-
posed to implement staged insertion and deletion of particles
for dense systems. Our method extends the concept of the
augmented ensembles developed by Kaminsky67 for the
grand canonical ensemble to the semigrand ensemble. Ac-
cordingly, the partition function for the augmented semi-
grand ensemble containing m 1 intermediate stages is given
as
m1
1
Y=
B3NN! i=0
N
i/midentities A dV dr2 drNeU+PV .
16
The system now consists of NA particles of species A,
N NA 1 particles of species B, and one particle in the in-
termediate particle i. There are m 1 stages of the interme-
diate particle. The intermediate stage is arbitrary but for
smooth interpolation it is chosen to be a hard sphere particle
with a diameter whose value lies between that of species A
and B. Each intermediate stage has a particular value of the
hard sphere diameter associated with it. The value of i in-
creases from 0 to m and the hard sphere diameter increases
accordingly. When the value of i equals 0, it corresponds to
species B and i = m corresponds to species A. We anticipate
that the intermediate particle diameters that give the best
results are those where the reversible work of increasing the
particle diameter is the same for each stage. As a first ap-
proximation, we choose particle diameters such that the in-
crease in volume of the particle between stages are equal. In
the augmented ensemble, the identity changes are carried out
only for the intermediate particle. During the identity change
 024508-5 Crystal nucleation in mixtures J. Chem. Phys. 125, 024508 2006

TABLE I. Simulation states and results for crystal nucleation in additive binary hard sphere systems. The first
line in the table corresponds to a pure component hard sphere system. P* = P3AA / kBT. = A B.

P* A xA n* G*

1.00 17.000 21.59 1.0 93 18

0.97 18.000 1.44 21.86 0.50 100 19
0.92 21.000 4.21 24.72 0.50 127 22
0.92 22.875 3.32 25.68 0.23 104 18
0.92 22.650 2.29 24.64 0.10 98 18
0.80 21.800 11.00 25.87 0.75 95 25

moves, the value of i is increased or decreased by 1. When
no intermediate particles are present, i.e., when i = 0 or i = m,
one particle is selected at random and the value of i is set to
0 if it belongs to species B or to m if it belongs to species A.
During simulations only contributions to the partition func-
tion when i equals 0 or m are considered. This yields correct
averages for the semigrand ensemble given by Eq. 14.
III. RESULTS AND DISCUSSION
We carried out Monte Carlo simulations to calculate the
properties of the critical nucleus in binary hard sphere fluids.
The calculations were performed for both additive and non-
additive binary hard spheres. For the case of additive hard
spheres, systems with = 0.97, 0.92, and 0.80 were studied.
The nonadditive hard sphere system studied had values of
= 1.0 and = 0.10. The choice of these systems was influ-
enced by the desire to study the effect of fluid composition,
fractionation, solid-solid immiscibility, and compound solid
formation. The states studied are listed in Tables I and II.
A. Additive hard sphere system
1. Nucleation in fluid mixtures
The first system that we studied was a binary hard sphere
mixture with = 0.97. The phase diagram for the
system,1113,50 recalculated by us, is shown in Fig. 1. Since
the size difference between the two components is very
small, the two components are completely miscible with
each other in both fluid and solid phases. The mixture is
close to ideal in the fluid phase and shows only mild nonide-
ality in the solid phase. The phase diagram is spindle shaped
and there is very little fractionation upon crystallization.
Such phase diagrams are formed by binary mixtures when
the two components are quite similar to each other. In this
case, the solid phase has a face-centered-cubic fcc structure
and at a given composition forms a substitutionally disor-
dered solid solution.1113,50 A pure fluid with diameter
freezes at P3 / kBT 11.7. At equilibrium, the solid phase is
richer in species A compared to the fluid. However, for the
current size difference of = 0.97, the extent of fractionation
is very small.
To compare the mechanism of crystal nucleation in a
mixture with that of the pure component, we carried out
simulations at pressures P* = PAA3
/ kBT 1.5P*f , where P*f is
the freezing pressure of the fluid. This corresponds to
roughly 33% supercooling. The total number of particles in
the system was 2916. Cluster size distributions were sampled
after every Monte Carlo trajectory which consisted of 20
displacements per particle, 10 volume moves, and 20 identity
changes per particle. In Fig. 2 we show a comparison of the
work of formation of the crystal nucleus for a fluid mixture
with mole fraction xA = 0.5 with that of the pure component.
Table I gives the numerical values from our calculations. The
curves show a maximum indicating that the fluid is meta-
stable and further growth of the crystal nucleus should lead
to a decrease in the free energy associated with a phase tran-
sition. We observe that the free energies of formation of the
nuclei are comparable for both the mixture and the pure
fluid. Figure 3 shows the composition of the crystal nucleus
as a function of its size. We can clearly see that the crystal
nucleus has a higher concentration of the larger species A
than the fluid indicating fractionation. Moreover we see that
the fractionation occurs for all sizes, both precritical and
postcritical, implying that fractionation of the components
precedes the occurrence of crystalline order. This fraction-

TABLE II. Simulation states and results for crystal nucleation for symmetric
nonadditive binary hard sphere systems with = 0.10. The first line in the
table corresponds to a pure component hard sphere system. P* = P3AA / kBT.
= A B.

P* B xA n* G*

17.0 21.59 0.0 93 18

18.5 9.75 22.86 0.1 164 31
21.6 9.30 25.54 0.2 170 35 FIG. 1. Phase diagram for a binary hard sphere system with size ratio
24.8 7.70 27.78 0.3 88 24 = 0.97. The solid phase denoted by the letter S is a substitutionally disor-
19.9 3.50 22.33 0.4 68 22 dered fcc crystal and the fluid phase is denoted by the letter L. The symbols
18.5 0.00 19.59 0.5 61 22 represent the coexistence points determined from simulations and the lines
are a guide to the eye.
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 024508-6 S. Punnathanam and P. A. Monson
FIG. 2. Comparison of the free energy barrier to crystal nucleation between
a pure hard sphere fluid solid line and a binary mixture dashed line with
= 0.97 and xA = 0.5, simulated at conditions shown in Table I.
ation should lead to an increase in the value of G* for the
mixture. However, the extent of fractionation in this mixture
is very small and the differences in G* between the mixture
and the pure fluid are smaller than the uncertainty in our
estimation of G*. We have also analyzed the structure of
the nuclei formed during simulations. In their simulations,
Auer and Frenkel27 found that for the pure hard sphere fluid,
the critical nucleus is made of up randomly stacked layers of
close packed hexagonal crystal planes. This structure is
called random hexagonal close packed structure RHCP.
Figure 4 is visualization of a cross section of the critical
nucleus for the fluid mixture which also exhibits the RHCP
structure. In the following sections, we show calculations of
G* for binary mixtures with smaller values of . These
systems show a much larger degree of fractionation upon
crystallization and thus provide good examples for studying
its influence on G*.
2. Nucleation in an azeotropic mixture
The next system that we considered had a value of
= 0.92. The phase diagram for this system is shown in Fig. 5.
Similar to the previous case the two components are com-
pletely miscible with each other in both phases. However, the
larger size difference leads to an increase in the nonideality,
especially in the solid phase, and the system now shows an
azeotrope at xA 0.23. Hence, when xA 0.23 then the solid
FIG. 3. Comparison of the composition of the crystal nucleus solid line
inside the metastable binary hard sphere fluid having = 0.97 with that to
the fluid dashed line and the corresponding stable solid dotted line. The
simulations are done at conditions given in Table I.
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FIG. 4. Color Computer graphics visualization showing a plane cut
through a configuration from a Monte Carlo simulation of a crystallizing
binary hard sphere mixture with size ratio = 0.97 and simulated at condi-
tions shown in Table I. Inside the nucleus, particles belonging to species A
are shown in white and those belonging to species B are shown in light gray
green. In the bulk, species A are shown in medium gray red and species
B are shown in dark gray blue. The hexagonal ordering of a 111 crystal
plane is evident in the cluster.
is richer in species A, when xA 0.23 the solid is richer in
species B and at the azeotropic composition the solid has an
identical composition to that of the fluid. Consequently, we
expect little fractionation to occur upon crystallization for
fluid with compositions close to the azeotropic composition.
Studying crystal nucleation in this system should reveal the
influence of fractionation upon G*.
We have calculated the nucleation barrier at points with
compositions that lie on either side of the azeotrope and at
the azeotropic composition. The calculations were carried
out at P* 1.5P*f . Again the simulations were performed on
2916 particles and each Monte Carlo trajectory consisted of
20 displacements per particle, 10 volume moves, and 20
identity changes per particle. Figures 6 and 7 show the free
energy change upon crystal nucleation and the composition
of the crystal nuclei as a function of the size of the nuclei,
FIG. 5. Phase diagram for a binary hard sphere system with size ratio
= 0.92. The solid phase denoted by the letter S is a substitutionally disor-
dered fcc crystal and the fluid phase is denoted by the letter L. There is an
azeotrope formation at xA 0.23. The symbols represent the coexistence
points determined from simulations and the lines are a guide to the eye.
 024508-7 Crystal nucleation in mixtures J. Chem. Phys. 125, 024508 2006

FIG. 6. Comparison of the free energy barrier to crystal nucleation between
a pure hard sphere fluid and a binary mixture with = 0.92 and simulated at
conditions shown in Table I. The compositions xA of the bulk fluid are 1.0
solid line, 0.5 dashed line, 0.23 dot-dashed line, and 0.1 dotted line. to fcc crystals of pure A and B components, respectively. The fluid phase is
respectively. The numerical values from these calculations
are listed in Table I. Based on these calculations we can
make a number of observations. G* is highest when xA
= 0.50 where correspondingly the degree of fractionation in
the cluster is also the highest. Near the azeotropic composi-
tion of xA = 0.23, the crystal nuclei formed during nucleation
have a composition similar to that of the fluid phase. In other
words, there is an absence of fractionation. This lack of frac-
tionation has a strong effect on the nucleation barrier. As we
can see from Fig. 6, the nucleation barrier at the azeotropic
composition is comparable to that of the pure component.
For the composition of xA = 0.10, the fractionation is now
reversed and the crystal nuclei are richer in component B
which is the smaller sphere. This behavior corresponds to
that of the phase diagram. However, the extent of fraction-
ation involved is very small and hence the nucleation barrier
is comparable to that of the pure component. These observa-
tions lead to the conclusion that crystal nucleation barriers in
mixtures are strongly influenced by the extent of fraction-
ation that is required prior to the formation of a crystalline
nucleus. Analysis of the structure of critical nucleus for each
of three cases show that they are comprised of hexagonal
layers particles randomly stacked one above another and thus
exhibiting a RHCP structure.
3. Nucleation in a system with a eutectic point
When = 0.80, the size difference between the two com-
ponents is so large that they become essentially immiscible
FIG. 8. Phase diagram for a binary hard sphere system with size ratio
= 0.80. The two components A and B are essentially immiscible in each
other. The solid phases are denoted by the letters A and B which correspond
denoted by the letter L. The eutectic point occurs at xA 0.23. The open
squares denote state points at which we were successful in studying nucle-
ation and the filled squares denote state point at which we were
unsuccessful.
in the solid phase. The phase diagram,50 shown in Fig. 8, has
a eutectic point at xA 0.23. For pressures P* between 11.7
and 28.0, the fluid mixture coexists with pure A or pure B
crystal. At higher pressures, the region of the phase diagram
corresponds to a two phase region of pure A and pure B
crystals in equilibrium with each other. This type of phase
behavior was found to be the most common in the survey by
Matsuoka.6 The state points at which nucleation simulations
were carried out are also shown in Fig. 8. These points cor-
respond to approximately 33% supercooling, i.e., P* P*f .
We were able to simulate the critical nucleus only at xA
= 0.75. This state point lies in the two phase region made up
of pure A crystal and the fluid mixture. For this mixture, the
chemical potential difference between the two species is very
large and hence, during simulations we used two intermedi-
ate stages to make identity changes between the species.
Thus during our simulations, on an average only one-third of
the configurations contained no intermediate particles. Hence
for these simulations, each trajectory was now defined as
consisting of six displacement moves per particle, three vol-
ume moves, and six identity changes per particle where only
those moves were considered where the configurations had
no intermediate particles. The total number of particles in our
simulations was 4000. The results are shown in Fig. 9 and

FIG. 7. Comparison of the composition of the crystal nucleus solid lines inside the metastable binary hard sphere fluid having = 0.92 with that to the fluid
dashed lines and the corresponding stable solid dotted lines. The simulations are done at conditions given in Table I. The figures correspond to bulk fluid
compositions xA of a 0.5, b 0.23, and c 0.1.
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 024508-8 S. Punnathanam and P. A. Monson
FIG. 9. Comparison of the free energy barrier to crystal nucleation between
a pure hard sphere fluid solid line and a binary mixture dashed line with
= 0.80 and xA = 0.75, simulated at conditions shown in Table I.
Table I. Again we see that the nucleation barrier is higher in
the case of the mixture than the pure component. Figure 10 is
a visualization of the critical nucleus. The core of the nucleus
is a pure RHCP crystal of particle A which corresponds to the
phase diagram. We were unable to calculate the nucleation
barriers for other state points shown in Fig. 8. The main
difficulty stemmed from the inability to grow crystal nuclei
from the fluid. Our repeated attempts to simulate nucleation
by varying the trajectory lengths and parameters in biasing
potential were unsuccessful. The reasons for the lack of suc-
cess using this method are not clear and further investiga-
tions will be needed to study crystal nucleation at these state
points.
B. Nonadditive hard sphere system
Crystal nucleation simulations were also performed on
binary mixtures of nonadditive hard spheres. Nonadditive
hard spheres are interesting because unlike additive hard
spheres, the compound solids formed by these systems show
FIG. 10. Color Computer graphics visualization showing a plane cut
through a configuration from a Monte Carlo simulation of a crystallizing
binary hard sphere mixture with size ratio = 0.80 and simulated at condi-
tions shown in Table I. The colors used are the same as those in Fig. 4. The
hexagonal ordering of a 111 crystal plane is evident in the cluster.
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J. Chem. Phys. 125, 024508 2006
FIG. 11. Phase diagram for a symmetric binary hard sphere system with
negative nonadditivity of = 0.10. Two types of solid phases occur. The
substitutionally disordered fcc solid solution is denoted by the letter S and
the substitutionally ordered compound solid with CsCl structure is denoted
by the letter R. The fluid phase is denoted by the letter L. The squares
indicate the state points at which the nucleation simulations were performed.
congruent melting/freezing. Congruent melting/freezing is
important because the compound solid can melt into a fluid
having the same composition. Thus congruent melting/
freezing enables us to study the dynamics of compound solid
formation from a supercooled fluid in the absence of other
phase transitions. Such phase behavior is the second most
common among binary organic mixtures.6 The compound
solids formed by additive spheres do not show congruent
melting/freezing and upon melting they undergo a phase
transition to form a fluid with different compositions and a
solid with different structures and compositions. Occurrence
of congruent melting/freezing for symmetric nonadditive
mixtures of binary Lennard-Jones particles was first shown
by Vlot et al.51 They showed that binary mixtures can form
substitutionally ordered solids that can exhibit congruent
melting/freezing. Such behavior is typical of chiral com-
pounds and study of these systems could yield insights into
the mechanism of solidification in chiral mixtures. We ex-
tended their ideas to compute the phase diagram of the more
simpler symmetric binary hard sphere mixture with negative
nonadditivity. In this model, AA = BB and = 0.1. The
computed phase diagram for this system is shown in Fig. 11.
As we can see, the phase diagram shows a double eutectic.
The system forms a substitutionally ordered solid at a com-
position of xA = 0.5. The compound solid has a CsCl structure
which is a body centered cubic structure with one type of
species at the eight corners of the cube and the other species
at the center of the cube. Moreover, the compound solid
shows congruent melting/freezing.
We performed crystal nucleation simulations at five dif-
ferent compositions of xA = 0.1, 0.2, 0.3, 0.4, and 0.5. The
calculations were performed at the same degree of supercool-
ing, i.e., at pressures P* = 1.5Pz*. These compositions were
chosen to study the influence of the eutectic point and the
effect of formation of the compound solid on nucleation. The
results from these calculations are shown in Table II. Figure
12 gives a comparison of the free energy of formation of
crystal nuclei inside a metastable fluid with composition xA
= 0.5 with that of the pure fluid. We immediately see a dif-
ference in the shapes of the two curves. This is an indication
that the structure of the nuclei formed when xA = 0.5 is dif-
 024508-9 Crystal nucleation in mixtures
FIG. 12. Comparison of the free energy barrier to crystal nucleation be-
tween a pure hard sphere fluid solid line and a symmetric nonadditive
= 0.10 binary hard sphere mixture dashed line with xA = 0.5.
ferent from that inside the pure fluid. Visualization of the
crystal nuclei formed when xA = 0.5 shows that they have the
CsCl structure see Fig. 13. We also observe from Fig. 12
that although there is no fractionation involved during the
nucleus formation, G* is higher for the mixture than the
pure fluid. This result is unlike that of nucleation in an azeo-
tropic fluid where the absence of fractionation leads to an
insignificant change in G* compared to the pure fluid. This
is because there is a compositional ordering of the two spe-
cies involved prior to formation of the crystalline solid. An-
other interesting observation for the xA = 0.5 case is that the
crystal nucleus has complete substitutional order right up to
its interface with the fluid. Or in other words, when ones
moves across the fluid-solid interface, not only do the par-
ticles exhibit translational order for a crystalline environment
but the two species also exhibit substitutional order with al-
most no intermediate behavior between the fluid and the
compound solid.
Figure 14 shows the free energy of crystal nucleus for-
FIG. 13. Color Computer graphics visualization showing a plane cut
through a configuration from a Monte Carlo simulation of a crystallizing
symmetric non-negatively additive binary hard sphere mixture with
= 0.10 and simulated at composition xA = 0.5 and at P* = 18.5. The colors
used are the same as those in Fig. 4. The compound CsCl structure is clearly
evident. For clarity, the particles are shown with a diameter AB.
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J. Chem. Phys. 125, 024508 2006
FIG. 14. Comparison of free energy barrier to crystal nucleation inside a
symmetric nonadditive = 0.10 binary hard sphere mixture at various
compositions for conditions shown in Table II. These compositions xA are
0.1 solid line, 0.2 dotted line, 0.3 dashed line, and 0.4 dot-dashed line.
mation inside the metastable fluid at various other composi-
tions and Fig. 15 shows the composition of the nuclei formed
compared with that of the bulk fluid and the solid. These
calculations show the effect of solid-solid phase separation
and the presence of the eutectic point on the mechanism of
crystal nucleation. When xA = 0.1 and 0.2, the compositions
of the nuclei are closer to the equilibrium composition of the
substitutionally disordered fcc solid than the substitutionally
ordered compound solid. The curves for G have shapes
similar to the pure component case indicating that the crystal
nuclei formed have a RHCP structure with substitutional dis-
order. We also see that the nuclei are richer in species B
which is consistent with the phase diagram. Visualizations of
the crystal nuclei confirm this observation. When xA = 0.4, the
composition is closer to that of the compound solid than the
fcc solid phase. The G curve is now similar to that for xA
= 0.5 indicating that the crystal nuclei have the CsCl struc-
ture. The direction of the fractionation is now reversed
Fig. 15 and the nuclei are richer in species A compared to
the fluid. Thus we can say that the structure of the nuclei is
strongly determined by the phase that is closer in composi-
tion to the fluid.
When xA = 0.3, the composition is very close to the eu-
tectic composition and there is a competing influence of both
types of solid phases. This provides a unique challenge in
simulating crystal nucleation since either one of the two solid
phases can crystallize or we can get a nucleus with a hetero-
geneous structure. The calculated G curve shown in Fig. 14
is different in shape from both the previous two cases and
looks like an intermediate between the two. The curve for the
composition dependence of the nuclei as a function of its
size Fig. 15 shows a crossover in the direction of fraction-
ation. The nuclei are richer in species B when n 20 and
vice versa when n 20. If it is consistent with the phase
diagram, this should indicate that the nuclei should have the
RHCP structure with substitutional disorder for extremely
small nuclei and the CsCl structure with substitutional order
for large nuclei. Visualizations of the larger nuclei show that
they have the CsCl structure. For smaller nuclei, the number
of particles was too few to arrive at a definite conclusion.
Our study of nucleation at the eutectic composition remains
inconclusive and further investigations are needed to under-
 024508-10 S. Punnathanam and P. A. Monson
stand the mechanism of crystal nucleation under these con-
ditions. The present result was obtained only when we ran
our simulations with equilibration periods that were three
times longer as compared to the other cases. For shorter
equilibration periods, we obtained nuclei with a heteroge-
neous structure, i.e., one that contained a mixture of regions
with RHCP structure and the CsCl structure. A similar result
was obtained in the work of Leyssale et al.73 The current
method does not distinguish the structure of the crystal nu-
clei formed during simulations and only requires that the
nuclei show crystalline order. This feature is very advanta-
geous in that fluid is free to crystallize into any structure and
the nucleation barrier is independent of our choice of order
parameters. However, this creates problems when studying
nucleation at eutectic compositions where two different
structures have similar free energies and we get nuclei with
heterogeneous structure. In order to determine more conclu-
sively the structure of the critical nucleus, we will have to
choose the order parameters that will force the system to
crystallize into a specific structure. The critical nucleus, by
definition, will be the one with the lowest free energy barrier.
IV. SUMMARY AND CONCLUSIONS
In this paper, we have presented our calculations of the
crystal nucleation barriers for wide variety of binary hard
sphere mixtures both additive and nonadditive. Unlike pure
fluids, the phase behavior for binary mixtures shows a vari-
ety ranging from simple spindle shaped phase diagrams to
those showing more complex behavior such as occurrence of
azeotropes, eutectic points, solid-solid immiscibility, and
compound solid formation. Our investigations show a sig-
nificant effect of the underlying phase diagram on the dy-
namics of crystal nucleation. Our calculations suggest that in
general, the nucleation barrier for mixtures is higher than
those for pure components under the same degree of super-
cooling. The composition of the solid phase is in general
different from that of the fluid. Hence crystal nucleation in
mixtures is preceded by fractionation of the components
which in turn increases the free energy barrier for phase tran-
sition. When fractionation is absent or small, e.g., crystalli-
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J. Chem. Phys. 125, 024508 2006
FIG. 15. Comparison of the composition of the nucleus
solid lines with that of the bulk fluid dashed lines for
the symmetric nonadditive = 0.10 binary hard
sphere mixture. The figures correspond to fluid compo-
sitions xA of a 0.10, b 0.20, c 0.30, and d 0.40.
The simulations are performed at conditions shown in
Table II.
zation at azeotropic composition, the nucleation barrier is
comparable to the pure component fluids. The role of frac-
tionation in increasing the difficulty of crystal nucleation has
been observed experimentally from crystal nucleation in col-
loidal systems.7476 Molecular dynamics simulations of crys-
tallization in binary hard sphere mixtures described in Ref. 3
also show this behavior.
We have also studied crystal nucleation of substitution-
ally ordered compound solids in a symmetric nonadditive
hard sphere mixture with = 0.10. The phase diagram for
this system shows two types of solid phases. A substitution-
ally disordered solid solution with fcc structure is formed
when one of the components is present in much larger quan-
tities but a substitutionally ordered solid with CsCl structure
is formed when the two species are present in equal quanti-
ties. During nucleation, the two crystal structures compete
with each other in order to determine the structure of the
nuclei. The structure of the nuclei is determined by the extent
of fractionation required to form the corresponding solid. We
found that the phase that nucleates is the one whose equilib-
rium composition is closer to the composition of the fluid
phase.
For future studies, we would like to investigate the role
of proximity to the eutectic composition on crystal nucle-
ation. As mentioned earlier, our attempts at studying crystal
nucleation for such systems both additive and nonadditive
hard spheres mixtures were only partially successful. It
would be also interesting to apply this method to study for-
mation of compound solids for additive binary hard sphere
mixtures,8 such as AB, AB2, AB13, etc., and the influence of
fractionation. Although in our simulations, we have not seen
nucleation of metastable phases, experiments9,10,77 on colloi-
dal systems have shown that it is possible to form metastable
solid phases if the fluid composition is closer to it. This
would allow us to investigate the validity of the Ostwald rule
of stages.78
ACKNOWLEDGMENT
This work was supported by a grant from the U.S. De-
partment of Energy Contract No. DE-FG02-90ER14150.
 024508-11 Crystal nucleation in mixtures J. Chem. Phys. 125, 024508 2006

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