An analysis of crystallization by homogeneous nucleation in a 4000atom softsphere

model
J. Neil Cape, John L. Finney, and Leslie V. Woodcock

Citation: The Journal of Chemical Physics 75, 2366 (1981); doi: 10.1063/1.442299
View online: http://dx.doi.org/10.1063/1.442299
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 An analysis of crystallization by homogeneous nucleation
in a 4000-atom soft-sphere model
J. Neil CapeS)
Department 0/ Physical Chemistry. Lensfield Road. Cambridge. England

John L. Finney
Department o/Crystallography. Birkbeck College. University 0/ London. England

Leslie V. Woodcock b)
Physical Chemistry Laboratory. University 0/ Amsterdam. Nieuwe Achtergracht 127, Amsterdam.
The Netherlands
(Received 17 March 1981; accepted 27 April 1981)

A molecular dynamics simulation of crystallization by the process of spontaneous homogeneous nucleation

fot a model of 4000 soft spheres with periodic boundary conditions is reported. When the amorphous system
in the metastable state, at a point for which classical homogeneous nucleation theory predicts a vanishing of
the free energy barrier, is annealed, many crystallites with variable symmetries are formed in the system. The
nature and structures of the growing crystallites are analyzed by examination of the primary Voronoi
polyhedra. The results support the qualitative correctness of the classical theory. Comparisons are made with
previous nucleation studies for the Lennard·Jones model at low temperatures and supercooled liquid metals
as studied recently by Raman and co-workers.

I. INTRODUCTION Voronoi polyhedra method of structure determinations

as described by Bernal and Finney.9,10 The technique
Rahman and co-workers - 3 have reported systematic
l
seemed to be more illuminating than studies of the in-
investigations of the process of spontaneous homo-
geneous crystallization of a supercooled Lennard-Jones tensity components of the structure factor used earlier
by Rahman and co-workers. 1-3
(LJ) liquid using the molecular dynamics (MD) technique,
following an initial accidental discovery of the pheno- More recently, Hsu and Rahman, 11,12 developing fur-
menon. Previous computer results for both hard4 and ther the Voronoi polyhedra method, have examined the
soft spheres 5 and shown that small systems readily com- effect of variations in the intermolecular potential on
press to quasicrystalline arrangements as an artifact the important question of what factors determine the ini-
of the periodic boundary conditions. Rahman's work, tial nucleite symmetry type. Alexander and McTague 13
however, with a larger 500-atom model indicated that have suggested, using theoretical arguments due to Lif-
the initial nucleation event occurs independently of the schitz, thatthe initial nucleite structure is invariably
boundary conditions, implying that most supercooled bcc. The results of Hsu and Rahman do not support this
liquids and especially simple atomic fluids should spon- conjecture, but rather demonstrate a complex dependence
taneously homogeneously nucleate when the circum- of the process of initial nucleite formation on the pair
stances are favorable, i. e., when both kinetic and ther- potential and suggest an important element of random-
modynamic barriers are small and when heterogeneous ness. In all these previous Simulations, however, only
nucleation mechanisms can be eliminated. a single nucleite has been observed in the system. The
indications are that very much larger systems are re-
Such conditions are especially easy to engineer in
quired both to eliminate periodic boundary effects on the
computer "experiments"; impurities and heterogeneities
growing crystallite and to assess the probability distribu-
can be absolutely excluded and there is no practical limit
tion for nucleites of various types for particular models.
to the quench rate or choice of potential function. Thus,
Rahman's work offers the first unambiguous "experi- In most of the earlier studies, the periodiC boundary
mental" evidence for the very existence of the pheno- effects have been discussed but not systematically in-
menon of homogeneous crystallization. Although a wide vestigated. In one of the simulations 7 the crystallite
variety of laboratory experiments have been reported, shape was markedly anisotropic and appeared to be
the interpretation of these crystallizations as being en- stabilized by the periodic boundary, spanning the entire
tirely homogeneous has been questioned. 6 Tanemura box width. Moreover, a bcc crystallite obtained for a
et al. 7,8 also inves tigated the kinetics of freezing in a Lennard-Jones system melted when the periodic boun-
model system of soft spheres using both 108- and 500- daries were removed. 3
particle systems and they obtained crystallites of both These observations constitute a strong case for the
bcc and fcc symmetry. Their work introduced the examination of much larger systems. In the present
paper, therefore, we report a study of homogeneous nu-
"'Present address: Institute of Terrestrial Ecology, Penicuik, cleation in a system of 4000 soft spheres as a continua-
Midlothian, Scotland. tion of a previously reported study of the glass forming
blAddress for correspondence. properties of this system.14 The salient results of this

2366 J. Chern. Phys. 75(5).1 Sept. 1981 0021·9606/81/172366·08$01.00 © 1981 American Institute of Physics
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 Cape, Finney, and Woodcock: Crystallization by homogeneous nucleation 2367

analysis are, first, an unequivocal demonstration of the

occurrence of nucleation and crystal growth, in a sys-
tem so large compared to the minimum stable nucleite
that boundary effects can be considered negligible.
Secondly, we observe many different nucleite types of
both bcc and fcc symmetry, and also icosohedral units
with fivefold symmetry, so-called "amorphous." 15
The general conclusion is that in bulk supercooled liquids
the process of homogeneous nucleation does occur, albeit
a very rare natural phenomenon, and is a complex and
unpredictable process. For any particular nucleation 151
event, however, the kinetics seem to be qualitatively in 150~-- ______ ________ ________
~ ~ __ ~~~ ~

accord with the predictions of classical homogeneous o 1000 2000 3000 Time Steps
nucleation theory.
FIG. 1. Variation of reduced pressure with time for the an-
II. SIMULATION METHOD nealing simulation; each time step is 0.005 mif IE.

The details of the method of simulation, the scaling

properties of the soft-sphere model, and the definition
longer fixed, or by the reduced pressure, which is now
of reduced units have all been described in detail be-
directly proportional to the internal energy. As the re-
fore 1•14 and need not to be reported here.
duced density is now constant, it is possible to specify
The final configuration of the 4000 particle system the most stable equilibrium crystal state towards which
from Ref. 14withp=2.7248, kT/E:=7.3593, andp* the system will relax. The initial and final states for
= 1. 831, was "annealed" with a time step of O. 005(mcfl / this simulation are given in Table I together with the
E:)1/2 for 3230 time steps. This took almost 10 h of most stable state at this reduced density, the fcc crys-
processing time on an IBM 370/165, or about 11 sec per tal.
iteration, using 290 kbytes of computer memory.
The relaxation process was monitored by calculating
The annealing of any rapidly quenched state allows the both equilibrium and dynamical properties as a function
system to relax to a state of lower potential energy. of time. Figure 1 shows the decrease in reduced pres-
For a molecular dynamics simulation, where the total sure with time. The values are calculated as time aver-
energy remains fixed, this would lead to a corresponding ages over 60, 80, or 100 time steps. Figure 2 shows
increase in kinetic energy. The properties of the soft- the mean square displacement of particles from their
sphere system depend only on a reduced density, which positions after 240 time steps as a function of time. If
is itself a dependent function of temperature, and so the slope of this graph in the central region is used to
simulation using the standard molecular dynamics tech- calculate an effective temporal self-diffusion coefficient,
nique does not maintain the system at constant reduced a value for DOff 14 of around 7 x 10-4 is obtained which is
density. The compressibility factor of the system at comparable to the value of a much lower density stable
time t would be related to the value at time t = 0 by1 fluid reported previously. 14
* 4 This system has a reduced density greater than that
(pV/ NkT)t = [(pV/NkT)o + 5] (~) - 5,
of the glass transition on MD time scales and clearly
shows the problems which arise when attempts are made
where pt and Pt are the reduced densities at time t = 0 to compute self-diffusion coefficients for insufficiently
and time t, respectively. If a state of the system given equilibrated systems. Spuriously high values are ob-
by [pt, (pV/NkT)o] were unstable, it would relax towards tained. The density of the present system is even great-
equilibrium along the path given by Eq. (1) provided that
the total internal energy remained constant.
The annealing procedure used here maintains the kine-
tic energy, and hence the temperature and reduced den
sity, constant by scaling the velocities at every time step. 10
Relaxation towards equilibrium may then be measured
by the decrease in total internal energy, which is no 8

4
T ABLE I. Initial and final properties of the annealed system.
2
Initial Final Equilibrium
Reduced density (p*) 1. 831 1.831 1. 831 o 1000 2000 3000 Time Steps
Reduced pressure ($) 156.0 152.1 137.3 FIG. 2. Mean-square displacement of atoms (beginning after
Structure amorphous crystallites fcc crystal 240 time steps) as a function of time for the annealing simula-
tion.

J. Chem. Phys., Vol. 75, No.5, 1 September 1981

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 2368 Cape, Finney, and Woodcock: Crystallization by homogeneous nucleation

er than that of the Kauzmann point of zero excess en- TABLE II. Distribution offl , the number of faces per poly-
tropy as determined previously, 14 yet even after anneal- hedron, for the initial configuration.
ing over several thousand time steps the diffusion is
finite and measurable. il 11 12 13 14 15 16 17
Frequency 2 88 473 830 492 141 21
III. METHOD OF STRUCTURE DETERMINATION Percent of total 0.1 4.3 23.1 40.5 24.0 6.9 1.0
A. Voronoi polyhedra method
The identification of a crystal nucleus in a fluid of
effectively the same density is not a trivial problem. face-center-cubic structure would have index (0, 12,
It the nucleus eventually grows it may be possible to 0, 0, ... ) and a body-center-cubic structure would have
use the structure factor to characterize the growth, 3 index (0, 6, 0, 8, 0, ..• ), where the zeros continue in-
but this method is only practical when the nucleus is definitely. For simplicity, the index may be written
well defined. When the nucleus or nuclei are in the pro- neglecting the zeros to the right of the last nonzero di-
cess of formation a more detailed method is required, git, i. e., (0, 12) and (0, 6, 0, 8) for the examples
and the work described here follows the method of Tane- above. Typical distributions of the Voronoi polyhedra
mura etal.,7 which is based on the local topology about for a fluid, a dynamic fcc crystal, and a dynamic bcc
each atom. crystal are given in Fig. 3. For selected indices the
To each atom i is ascribed a "Voronoi polyhedron" distribution is markedly different for each of the three
(VP j) which bounds the region of space which is closer cases. As expected, there is no particular index typi-
to atom i than to any other atom. The faces of VP I lie cal of the fluid structure, whereas for the bcc crystal
within the planes which perpendicularly bisect the lines the proportion of (0, 6, 0, 8) polyhedra is very large.
joining atom i to neighboring atoms j. The volume de- Any others arise from vibrations about the lattice points
fined by VP I is a measure of the local atomic volume, which distort the local symmetry. The rhombic dode-
and the set of all the VP I fills the total volume uniquely. cahedra of a perfect fcc lattice are destroyed by any
The Voronoi polyhedra may be regarded as generalized kind of Vibration, and give rise to polyhedra with in-
Wigner-Seitz cells. If the total number of faces of VP I dices such as (0, 3, 6, 4), (0, 3, 6, 5), (0, 4, 4, 6),
is given by II> then/i represents a local geometrical co- (0, 4, 4, 7), etc. The types of Voronoi polyhedra
ordination number. The local configuration about atom which are found for a given configuration are indicative
i can be described by the number of edges of each of the of the short-range structure and the spatial distribution
faces of VP;, and may be indexed, following Finney, 5 by of related Voronoi polyhedra reflects the long-range
listing the number of faces having 3,4,5, .•. edges. The structure.
set of integers n 3, n4, n5, •.• , where I", n", =Ii describes For example, a nucleus with bcc symmetry is charac-
the detailed atomic arrangement around atom i. A perfect terized by Voronoi polyhedra of type (0, 6, 0, 8) or
(0, 4, 4, 6) which are contiguous to another polyhedron
of type (0, 6, 0, 8). A perfect fcc (or hcp) crystal gives
rise to a polyhedron of type (0, 12), but since this type
freq involves vertices at which four, rather than three, edges
% meet, it is transformed into a variety of different types
b.c.c. cry st a I
by the small distortions arising from thermal vibrations.
(=1.51 10 Although techniques existl1 for referring to the ideal fcc
polyhedron type, their application is not, at present, un-
o+---~~--~~--~~~ equivocal and cruder methods, as described in Sec. HID
below, were used to confirm the nucleus with fcc sym-
20
metry in the present work.
f.c.c. cry st a I
~*=1.50 10 B. Structure of the initial and annealed configurations
The atomic positions of the initial configuration were
O~~~~LL~~~-W~~
used to calculate the Voronoi polyhedra for the con-
20 figuration. Only those polyhedra which did not cross
fluid the periodic boundaries of the system were considered.
,"=1.12 10 This was to expedite the computational analysis since
the actual pOSition of the reference frame for the period-
ic boundary is entirely arbitrary.
Figure 4 shows the distribution of index types; a com-
parison with Fig. 3 shows no significant evidence of an
increase in the numbers of polyhedra associated with a
particular type of crystal structure. The distribution is
not identical to that of Fig. 3 because the reduced densi-
FIG. 3. Distribution of selected types of Voronoi polyhedra ties are different. The number of faces per polyhedron,
for the equilibrium fluid, fcc crystal, and bcc crystal. i. e., the distribution of Ii is given in Table II. The

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 Cape, Finney, and Woodcock: Crystallization by homogeneous nucleation 2369

15 20 Freq t g( r)

o 1 2 3
FIG. 6. Pair distribution function for the initial configuration.

FIG. 4. Distribution of selected types of Voronoi polyhedra The pair distribution function g(r) for the initial con-
for the initial configuration. figuration is shown in Fig. 6. This is typical of a highly
supercooled liquid or amorphous structure, with a split
second peak and with no signs of peaks or shoulders cor-
mean local coordination number so defined is 14.09, and responding to the lattice spacings of crystal structures.
the distribution of polyhedron volumes about the mean Taking into account the distribution of the polyhedral
is shown in Fig. 5. types, the absence of bcc nuclei and the absence of any
evidence of crystallinity in the pair distribution function,
Analysis of the initial configuration in terms of possi- it appears that the initial configuration is wholly amor-
ble bcc nuclei using the criteria described above gives phous in character.
only one group of atoms with more than ten members.
This group contains only three atoms of type (0, 6, 0, 8), Two further analyses in terms of the Voronoi poly-
and cannot be regarded as a potential crystal nucleus. hedra were performed after annealing. The first was
As both previous simulations have found bcc structures for the single configuration after 3180 time steps, and
occurring before fcc structures, even though the latter the second for the time-averaged atom positions over the
are the more stable crystalline forms for the bulk crys- period 3181 to 3230 time steps. The latter procedure
tal, no attempt was made to locate groups of atoms with reduces the effects of atom vibrations about fixed points.
fcc symmetry. The resultant polyhedron statistics were virtually iden-
tical, and the following results are based on the data
from the time-averaged configuration.
The distribution of polyhedron types, shown in Fig. 7,
freq is now quite different from that of the initial configura-
% tion (Fig. 4), and comparison with Fig. 3 suggests ele-
5 ments of both bcc and fcc structure. There is a marked
increase in the number of (0, 6, 0, 8) polyhedra, typical
4 of a bcc structure, and in the numbers of (0, 4, 4, 6) and
(0, 4, 4, 7) polyhedra, which may be related to fcc sym-
3 metry. The distribution of 1/ is given in Table III, and
the proportion of polyhedra with 16 or 17 faces is seen
2 to be smaller than for the initial configuration, although
the mean local coordination number is almost the same,
at 14. 05. The distribution of polyhedron volumes is
given in Fig. 8, and shows a smaller spread and a skew
O~--~~~~--------r-------~~~--------
0.9 1.0 1.1 VOlume/v towards smaller volumes when compared to the initial
configuration.
FIG. 5. Distribution of Voronoi polyhedra volumes about the
mean for the initial configuration. The pair distribution function (Fig. 9) is similar to

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 2370 Cape, Finney, and Woodcock: Crystallization by homogeneous nucleation

Ii index 5 10 15 20 Ireq%0
freq
12 0012 r.
13 ,,1102
5
0283
0364 I 4
0445
0526
~ 3441
0 2
3

14 0284 I
10365 I
0446 I
0608 I O~--------~~-------r------~~~-------
0·9 1·0
1264 II 1·1 VOlume/V

15 0285
~345 1 FIG. 8. Distribution of Voronoi polyhedra volumes about the
mean for the initial configuration.

0366 'I
0447 I If the whole system had a perfect bcc structure, then
0528
13461
l-J the edge of the cubic unit cell would have length 0.0794l,
where l = V l/3 • The direction cosines and lattice
all ot hers I constants for each of the three largest nuclei are given
in Table IV. The direction cosines of the cubic unit cell
FIG. 7. Distribution of selected types of Voronoi polyhedra are calculated as averages over the 12 edges of each
for the final configuration. unit cell. It is clear from the data in Table IV that the
nuclei are not correlated with each other in that the di-
rection cosines are different in each case. This sug-
that for the initial state. There is a slight shoulder on gests that the 4000-atom system is big enough to observe
the second peak at r= 1. 3 a(E:/kT)1/12, and the splitting homogeneous nucleation free from the effects of periodic
of the second peak is more pronounced, but the pair boundaries. The direction cosines in each case define
distribution function is seen to be relatively insensitive axes which are orthogonal to within the statistical un-
to the changes in detailed structure as shown by the dis- certainty, and the side length of the cubic unit cell is as
tribution of polyhedral types. expected. The relative positions of the atoms within
each of the nuclei is shown in Figs. 10 and 11, where
The analysiS in terms of contiguous polyhedra of type
the coordinates are plotted as a projection along the cube
(0, 6, 0, 8) gives the clearest indications of crystallinity
In all, seven groups each containing more than 20 atoms'
with polyhedra of types (0, 6, 0, 8) or (0,4, 4, 6) were
found, the largest of which had 41 members, including
19 of type (0, 6, 0, 8). The three largest groups are g(r)
described in detail in the next section, and groups with
fcc symmetry are discussed in Sec. IUD. 5

C. Nuclei with body-center-cubic symmetry

The method used to identify bcc nuclei, as described
4
above, gives an underestimate of the size of a nucleus,
as it only considers those atoms whose Voronoi poly-
hedra have symmetries typical ofa bcc solid. In general,
each atom having such a "perfect" site is surrounded by 3
other atoms which themselves may lie on lattice sites.
The method does not therefore include in the nucleus the
outer "layer" of atoms, but only the perfect central core.
2

TABLE III. Distribution off" the number of faces per poly- 1

hedron, for the final configuration.

f, 11 12 13 14 15 16 17
Frequency 47 473 961 468 81 11 o 1 2
Percent of total 0.0 2.3 23.2 47.1 22.9 4.0 0.5
FIG. 9. Pair distribution function for the final configuration.

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 Cape, Finney, and Woodcock: Crystallization by homogeneous nucleation 2371

TABLE IV. Properties of the three largest bcc nuclei.

Size Direction cosines Lattice constants

1 41 x 0.482 0.876 -0.030
Y 0.50:l -0.303 -0.810 O. 079 ± O. 006 1
z 0.749 -0.361 0.556

2 38 x -0.252 0.965 -0.073

Y 0.615 0.227 0.755 0.080±0.0061
z -0.737 -0.063 0.673
3 36 x 0.998 - O. 050 -0.024
Y 0.031 -0.676 0.736 0.078±0.0061
z -0.070 0.700 0.711

diagonal of the unit cell. Solid lines denote the edges of

the two interpenetrating simple cubic lattices, and dashed
lines have been drawn between nearest neighbor positions
as shown diagrammatically in Fig. 12.
FIG. 11. A nucleus with body-center-cubic symmetry contain-
D. Nuclei with face-center-cubic symmetry
ing 36 atoms.
There is no easy method of identIfying regions with
fcc symmetry, as there is no one characteristic type of
Voronoi polyhedron. There is , however, a set of poly- neighbors were examined as well. Several groups of
hedra which may be formed by slight distortion of the atoms were identified which appeared to have the re-
rhombic dodecahedron which is the polyhedral type in the quired symmetry. Only one of these was examined in
perfect static fcc lattice. The positions of all atoms detail. The whole nucleus, including atoms on surface
having Voronoi polyhedra of types (0, 4, 4, 6), (0, 4, 4, sites, contains 147 atoms, and the direction cosines and
7), (0, 3, 6, 4), (0, 3, 6, 5), and (0, 3, 6, 6) were lattice constants are given in Table V. The axes so de-
listed, and a table was compiled of all pairs of such fined are orthogonal to within better than 1%.
atoms separated by a distance of 0.0951 to 0.1051,
where l = (VI N)1/3. The edge length of the four inter- A projection of the atom positions along the space dia-
penetrating Simple cubic lattices which form the fcc gonal of the cubic unit cell is shown in Fig. 13. The
structure would be 0.1001 if the whole system had a per- lines connect atoms on the four simple cubic lattices,
fect fcc structure. The relative direction cosines for as shown in Fig. 14. Although the nucleus so defined is
each pair were then listed, and atoms having at least not perfect, as may be seen from Fig. 13, it is apparent
three orthogonal partners were deSignated as possible that there is a region having fcc symmetry which has
members of a fcc nucleus. All the neighbors of each of been formed spontaneously during the annealing process.
these atoms were then examined to establish any con-
tinuation of the lattice defined by the atom at the center E. Structures with fivefold symmetry
of the three orthogonal axes. If any of these neighboring There has been a suggestion 9 that a glassy state should
atoms were found to fall on the lattice, then all their contain structural units possessing fivefold symmetry,
and examples of possible "noncrystallographic" struc-
tures have been cited. The easiest of these structures
to identify by means of the Voronoi polyhedra are those

/ ' prOjection

FIG. 10. A nucleus with body-center-cubic symmetry contain-

ing 41 atoms; the solid lines connect atoms as the same simple-
cubic lattice and dashed lines connect the nearest neighbors. FIG. 12. Projection along the space diagonal of the bcc lattice
The projection is along the space diagonal of the unit cube. unit cube.

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 2372 Cape, Finney, and Woodcock: Crystallization by homogeneous nucleation

TABLE V. Properties of nucleus with fcc

symmetry. /projection
Direction cosines Lattice constant
x 0.97 - 0.17 - O. 17 0.099±0.0051
Y 0.21 0.95 0.23 0.102±0. 0041
z 0.13 -0.25 0.96 0.101 TO. 0061

based upon a perfect icosahedron, and although large

structures possessing fivefold symmetry are not to be
expected ina periodic system, the initial and final con-
FIG. 14. Projection along the space diagonal of the fcc lattice
figurations were examined for icosahedral structures. unit cube.
A perfect icosahedron has index (0, 0, 12), and the ini-
tial configuration was found to have 26 such Voronoi poly
hedra, The basic icosahedron is determined by the po- sahedral Voronoi polyhedra. One of these clusters con-
sitions of 13 atoms, one at the center, and one for each taining 59 atoms is shown in Fig. 15. Other structures
of the 12 pentagonal faces. The positions of these atoms having fivefold symmetry undoubtedly exist in both the
and their nearest neighbors are shown for one of these initial and final configurations, but it is not possible to
icosahedral centers in Fig. 15 as a projection along an identify them easily by means of the Voronoi polyhedra
axis passing through the central atom and the centers of alone.
two of the parallel faces of the icosahedron. Lines have
been drawn between pairs of atoms separated by less IV. TEST OF CLASSICAL NUCLEATION THEORY
than 0.085l, where 1 = V 1/3 • The first peak in the
pair distribution function is centered at O. 071, width The classical theory of homogeneous nucleationt7 has
0.06l to 0.091. This cluster contains 61 atoms, and is been shown to agree with experiment to an accuracy
clearly seen to have elements of fivefold symmetry. If which must be the result of canceling errors, in view of
every icosahedral Voronoi polyhedron has associated the assumptions and Simplifications involved. However,
with it a cluster of this size having fivefold symmetry, it is instructive to consider its predictions in the light of
then structures of this type would account for three- the present results.
quarters of the total volume of the system, in accord The excess Gibbs free energy of small crystrallites is
with Hoare's theory of amorphous structures. 16 expressed in terms of bulk thermodynamic quantities.
If nucleation to crystallographic symmetries is occur-
For a crystallite of n atoms
ring as annealing proceeds, then structures with fivefold
symmetry should decrease in number. This is true for
the simulated system, in that the final configuration has
only nine structural units which clearly relate to ico-

FIG. 13. A nucleus with face-center-cubic symmetry contain-

ing 147 atoms. The solid lines connect atoms on the four inter- FIG. 15. A cluster with fivefold symmetry containing 61 atoms
penetrating simple cubic lattices. The projection is along the from the initial configuration. The central icosahedral atoms
space diagonal of the unit cube. are shaded.

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 Cape, Finney, and Woodcock: Crystallization by homogeneous nucleation 2373

TABLE VI. Predictions of classical nucleation tion can be derived from the forgoing analysis.
theory.
Previous simulations of crystallization have been per-
p* p nmu tl.C e (nm;a)!kT formed on systems with 500 atoms or fewer, and with
periodic boundary conditions, and only a single crystal-
1. 20 26.34 1503 93.6
1. 25 30.75 117 16.7 lite has been observed. It has not been clear to what
1. 30 35.75 23 5.5 extent this nucleation was induced by the periodic bound-
1.409 48.88 1. 93 1.0 ary although it has been suspected that it plays a domi-
1.445 54.16 1. 00 0.63 nant role for small systems. The present results show
1. 831 152 0.005 0.016 unequivocally that homogeneous nucleation is a natural
process in a large system and that it occurs independent
ly of the periodic boundary.
tl.C e (n) = YC-L A(n) + (J.1.e - J.1.L) n ,
These findings accord quantitatively with the predic-
where A is the surface area 41T(3V/41TN)2/3 n2/ 3 and tions of classical homogeneous nucleation theory. Ther,
YC-L is a value for the interfacial tension averaged over appears to be virtually no barrier to the occurrence of
all possible oreintations of the interface; J.1. is the chemi- the spontaneous nucleation observed in our computation~
cal potential in each phase. The approximation usually the only retarding factor seems to be the relaxation tim,
made is that the enthalpy of fusion is independent of tem- for cooperative translational diffusion. The height of th
perature, so that, from the Gibbs-Helmholtz relation, barrier at the density and temperature which it occurs
d(J.1.c - J.1.L)/ dT = tl.H,/ NT is predicted to be much less than kT by the classical
treatment.
and integration gives
J.1.e - J.1.L = (tl.H,/ N) In{T/T,) ,
In addition to the many bcc nucleites, a fcc nucleite
has been confirmed thus casting doubt on the "Ostwald
as J.1. e = J.1.L at T = T,. step rule,,3 that the first stage in phase transformation
This gives is to that phase of second lower stability and not to the
tl.Ce{n) A (n) tl.H, )
most stable. The most stable phase of the soft-sphere
--;;r- =---;;:r- YC-L + n NkT In(T/T, • crystal is the fcc.

Differentiation to find the maximum value of tl.C e as a

function of n, the ''barrier'' to nucleation, gives the size
of the critical nucleus as
IA. Rahman, M. J. Mandell, and J. P. McTague, J. Chern.
(W Y~_L(41T)3 (3 V/41TN)2 Phys. 64, 1564 (1976).
1Zrnu = (tl.S,/ Nk)3 (T,/T In(T,/T))3 2M. J. Mandell, J. P. McTague, and A. Rahman, J. Chern.
Phys. 64, 3699 (1976).
and substituting, for YC-L a value of y = O. 5 18 for (tl.S,/ Nk) 3M. J. Mandell, J. P. McTague, and A. Rahman, J. Chern.
a value of 0; 9,19 gives Phys. 66, 3070 (1977).
4B . J. Alder and T. E. Wainwright, J. Chern. Phys. 33, 143£
1Zrnax = 5. 746 p*-2/ (T,/ T)3 (In (T,/T)j3 • (1960).
For a system at constant pressure p, 5W. G. Hoover, S. G. Gray, and K. W. Johnson, J. Chern.
Phys. 55, 1128 (1971).
i. 995x 104 6See , for example, D. P. Woodruff, The Solid-Liquid Interface
(Cambridge University, Cambridge, England, 1973), Chap.
1M. Tanernura, Y. Hiwatari, H. Matsuda, T. Ogawa, N.
and Ogita, and A. Ueda, Prog. Theor. Phys. 58, 1079 (1977).
8M. Tanernura, Y. Hiwatori, H. Matsuda, T. Ogawa, N.
Ogita, and A. Ueda, Prog. Theor. Phys. 59, 323 (1978).
9J • D. Bernal and J. L. Finney, Discuss. Faraday Soc. 43,
60 (1967).
+ Yp.-2/3 41T(3/ 41T)2/3 n!!.! . IOJ. L. Finney, Proc. R. Soc. LondonSer. A 319, 479
(1970).
Table VI gives some values of 1Zrnu. and tl.C 6 (1Zrnu) as a IIC. s. Hsu and A. Rahman, J. Chern. Phys. 70, 5234 (1979).
function of P*, where the p values are obtained from 12C. S. Hsu and A. Rahman, J. Chern. Phys. 71, 4974 (1980).
Ref. 14. Also given are the appropriate values for 13S. Alexander and J. P. McTague, Phys. Rev. Lett. 41, 702
the annealing simulation. The formation of stable nuclei (1978).
should occur when ACejkT becomes of the order of unity, 14J. N. Cape and L. V. Woodcock, J. Chern. Phys. 72, 976
which in this case would mean a critical size for the nu- (1980).
cleus of 10-20 atoms. For the state with reduced density 15J. A. Barker, M. R. Hoare, and J. L. Finney, Nature (Lon-
don) 257, 120 (1975).
p* = 1. 831 considered here, the thermodynamic barrier 16M. Hoare, Ann. N. Y. Acad. Sci. 279, 186 (1976).
to homogeneous nucleation as predicted by this simple 17 See , for example, J. Frenkel, Kinetic Theory of Liquids
theory is negligible. (Dover, New York, 1955), Chap. 5.
18J. N. Cape and L. V. Woodcock, J. Chern. Phys. 73, 2420
V. CONCLUSIONS (1980).
19W . G. Hoover, M. Ross, K. W. Johnson, D. Henderson,
A number of definite conclusions regarding the pro- J. A. Barker, and E. C. Brown, J. Chern. Phys. 52, 4931
cess of homogeneous nucleation vis a vis glass forma- (1970).

J. Chern. Phys., Vol. 75, No.5, 1 September 1981

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