Statistical geometric analysis of

hard-sphere microstructures
V. Senthil Kumar
Advisor: Prof. V. Kumaran
Department of Chemical Engineering
Indian Institute of Science
Outline 1
Theme: Statistical geometry is useful for deriving structure-
property correlations, characterizing the microstructures
and locating structural transitions.
Introduction
- Hard-disks & Hard-spheres,
- Voronoi tessellation
Cell-volume distribution Congurational entropy
Equilibrium neighbor statistics EHSD of LJ uid
Sheared neighbor statistics Non-equilibrium transitions
Bond-orientational analysis Martensitic transformation
Characterization of microstructures 2
m = 9.44 m = 5.72
Aim: To develop measures of microstructural randomness
and utilize them to characterize the state and quantify the
properties.
Hard-disks & Hard-spheres
- Introduction
Hard-disk uid/solid 3
= 0.50 = 0.78
HD system: elastic collisions of rigid disks in two-dimensions.
Simplest continuous system with freezing/melting transition,

F
0.691,
M
0.716.
No microscopic energy scale. All non-overlapping congurations are
permissible. Statistical geometry Properties
HD system model for monolayers. HS system reference uid for real
liquids, accounts for exclusion eects.
There are metastable congurations and glass transition

too.
Hard-disk/sphere properties 4
v = specic volume
v
p
= volume of a particle
=
v
p
v
, packing fraction
v
c
,
c
= volume, packing fraction at closed packing
y =

c
, normalized packing fraction
hard rod hard disk hard sphere
is length diameter diameter
v
p


4

2
6

3
v
c

3
2

2 1

F
- 0.691 0.494
s
F
/k - 0.36 1.16

M
- 0.716 0.545

LRP
- 0.772 0.002 0.555 0.005

DRP
- 0.82 0.02 0.64 0.02

c
1

2

2
Voronoi tessellation - Introduction
Poisson Voronoi Tessellation 5
Point = particle center, departmental store etc.
Convex space-lling polygons formed by the perpendicular
bisectors
Any point inside the Voronoi polygon is closer to its nuclei
than any other nuclei - denition of local volume
Geometric neighbors are the competing zones
Hard-disk Voronoi tessellation 6
As approaches
c
Voronoi cells become regular
Useful framework to analyze all structures, random to regular
Geometric denition of local volume and neighbors
Occurrence: Crystallization, plant cells 7
Source: www
All nuclei appear simultaneously and xed during growth
Isotropic, linear growth rate
Growth ceases when a cell comes in contact with a neigh-
boring cell
Utility: Microstructural characterization 8
Applications
Microstructural analysis of packings, glass, foam, cel-
lular solids, proteins etc. Widely used in Meteorology,
Geology, Ecology, Metallography, Archeology.
Properties Typically Studied Zhu et al. (2001)
Distribution of cell-volume, number of neighbors, cell
surface area, vertex angles etc.
We show that Voronoi statistics are useful in character-
izing the microstructures and estimating the properties.
Cell-volume distribution and
congurational entropy of
hard-spheres
J. Chem. Phys. 123, 114501 (2005).
Congurational entropy 9
Partition Function, Q =
_
2mkT
h
2
_
D N
2
Q
conf
Cong. Integral, Q
conf
=
1
N!
_
V

_
V
exp( U) dr
1
dr
N
F = kT logQ; F
conf
= kT logQ
conf
S =
_
F
T
_
N,V
; S
conf
=
_
F
conf
T
_
N,V
S = S
conf
+
D
2
Nk log
_
2mkT
h
2
_
+
D
2
Nk
S
conf
contains all the thermodynamic information
Free-volume theory 10
Kirkwood (1950) by spatial coarse-graining showed that
s
conf
= s
cell
+s
com
.
() Cellular entropy s
cell
single occupancy of regular
cells.
() Communal entropy s
com
multiple occupancy of reg-
ular cells.
Cohen and Grest (1979) assumed the same partitioning
for the Voronoi irregular cells.
() Ansatz s
cell
= k
_
f(v) log[f(v)]dv, in analogy with
mixing entropy of binary uids.
() Communal entropy s
com
due to the existence of uid
clusters.
() Used in the theory of supercooled liquids.
Aim: To check the validity of Cohen-Grest ansatz for the
hard sphere system. First, we will focus on f(v).
Poisson cell-volume distributions 11
0 0.5 1 1.5 2 2.5 3 3.5
0
0.2
0.4
0.6
0.8
1
v
f
(
v
)
0 0.5 1 1.5 2 2.5 3
0
0.2
0.4
0.6
0.8
1
v
f
(
v
)
2D 3D
f(v) =

m
(m)
v
(m1)
e
v
; v =
m

D m Reference
1 2 Exact result, Kiang(1966)
2 3.61 Weaire et. al (1986)
2 3.57 DiCenzo and Wertheim (1989)
2 3.578 Current work
3 5.56 Andrade and Fortes (1988)
3 5.562 Current work
Hard-disk cell-volume distributions 12
0.85 0.9 0.95 1 1.05 1.1
0
2
4
6
8
10
12
14
16
18
v
f
(
v
)
HD, = 0.82
close packed cell-vol = v
c
Voronoi cell-vol, v v
c
Free-volume: v
f
= v v
c
f(v
f
) =

m
(m)
v
(m1)
f
e
v
f
Specic volume condition: v
f
=
m

= v v
c
Fitting for v
f
, approximately compensates the steric eects
Regularity factor 13
0.8 0.9 1 1.1 1.2 1.3 1.4
0
5
10
15
20
25
30
v
f
(
v
)
=0.65
=0.70
=0.75
=0.80
=0.85
=0.90
0.8 1 1.2 1.4 1.6
0
2
4
6
8
10
v
f
(
v
)
=0.70
=0.75
=0.78
=0.80
=0.82
=0.84
TD Rnd
Relative spread=
Std. dev
Mean
=
1

m
As cells become regular
Std.dev
Mean
, m
Dense TD structures approach Dirac-delta distn, , m
Dense Rnd structures approach exponential distn, , m
HD/HS Regularity factors 14
0 0.2 0.4 0.6 0.8
0
2
4
6
8
10
12
14
16

m
NVE
Rnd
0 0.2 0.4 0.6
0
10
20
30
40
50

m
NVE
Rnd
On freezing, due to the onset of order, m increases sharply.
TD structures: , m
Low density Rnd structures identical to TD structures.
Regularity factor is a structural order parameter. It distinguish dense
thermodynamic and dense random structures.
Dense Rnd structures: , m . Can we explain this?
Maximum-entropy formalism 15
Information entropy:
s
I
= k
_

v
c
f(v) log[f(v)]dv = k
_

0
f(v
f
) log
_
f(v
f
)

dv
f
s
I
/k = log[v(1 y)] +(m), where
(m) = (m1)(m) +log[(m)] log(m) +m.
s
I
is a functional of m. Setting
s
I
m
= 0 gives m = 1.
Exponential distn is maximally random.
Notion of order: equality of cell vols
Max disorder: exponential distn.
Least information state: Close packing crystal unit cell.
Moderate info state : Ideal gas Rnd number generator.
Maximum info state : Dense Random Packing (or jammed states).
Excess Info Ent : s
ex
I
/k = log(1 y) +(m) (m
0
)
the reference ideal gas is at same specic volume.
Structural inhomogeneities near DRP 16
0.85 0.9 0.95 1 1.05 1.1
0
2
4
6
8
10
12
14
16
18
v
f
(
v
)
0.9 1 1.1 1.2
0
2
4
6
8
10
v
f
(
v
)
HD = 0.82, N=256, conf=10
4
HD = 0.82, N=256, conf=1000
Structural inhomogeneities due to DRP algorithm poor t
Binodal f(v) dense and lean regions.
Large-volume tails Line defects(2D) or planar defects(3D).
Speculation: An ideal DRP algorithm producing homogeneous struc-
tures might exactly realize the max-ent prediction.
Cellular entropy 17
Cohen-Grest ansatz: s
cell
= k
_
f(v) log[f(v)]dv
Info ent: s
I
= k
_

v
c
f(v) log[f(v)]dv = k
_

0
f(v
f
) log
_
f(v
f
)

dv
f
s
ex
I
/k = log(1 y) +(m) (m
0
)
Modied ansatz: s
ex
cell
= s
ex
I
s
ex
cell
/k = [log(1 y) +(m) (m
0
)]
For the ansatz to be useful, should be a density-independent con-
stant.
s
conf
= s
cell
+s
com
.
s
com
due to the existence of uid clusters.
As
c
, no uid clusters. Hence s
com
0 and s
conf
s
cell
.
We use this asymptotic limit to estimate .
Alder et al. (1966), Z = D/a +c
0
+c
1
a + , where
a = (v v
c
)/v
c
= (1 y)/y is the fractional excess free-volume.
Using Z expression in s
ex
conf
/k =
_
y
0
Z1
y
dy,
gives s
ex
conf
/k = Dlog(1 y) (c
0
c
1
1) logy +c
1
/y + .
Comparing the dominant terms, we get = D.
This identication is independent of the gamma t and is valid for
any short-ranged force model.
Cellular entropy 18
0 0.2 0.4 0.6 0.8
15
10
5
0

s
v E
/
k
Vor
Virial
Composite
0 0.2 0.4 0.6
15
10
5
0

s
v E
/
k
Vor
Virial
Composite
HD HS
With = D, the cellular entropies are nearly equal to the congura-
tional entropies for densities above freezing.
s = s
conf
+
D
2
k log
_
2mkT
h
2
_
+
D
2
k
The last two terms arising from integration of momenta are
rst-order homogeneous is D.
Toy model: HS in a box, x, y, z, No. of states=2
D
.
N independent HSs, = (2
D
)
N
= 2
ND
S = k log = NDlog2.
Summary: Cell-volume distributions 19
m is a structural order parameter, which distinguishes
dense thermodynamic and dense random structures.
If number of states 2
D
, then entropy is rst-order ho-
mogeneous in D. We have found a factor of D correction
to Cohen-Grest Ansatz, s
cell
= kD
_
f(v) log[f(v)]dv.
This identication is independent of the gamma t and
is valid for any short-ranged force model.
For dense liquids, congurational entropy is mostly cel-
lular. For athermal systems like an ensemble of similarly
prepared powders, communal entropy is identically zero.
Hence cellular entropy solely denes the state.
Neighbor statistics and
eective hard-sphere diameter of
a Lennard-Jones uid
J. Chem. Phys. 123, 074502 (2005).
Voronoi partitioning of g(r) 20
0 2 4 6 8
0
0.5
1
1.5
2
2.5
3
3.5
r
g
(
r
)
g1
g2
g3
g4
gsum
Rahman (1966)
g(r) =
(r)

=
N(r, r +r)
V (r, r +r)
N(r, r +r) = N
1
(r, r +r) +N
2
(r, r +r) +
g(r) = g
1
(r) +g
2
(r) +
Relation between f
n
(r) and g
n
(r) 21
g
n
(r) =

n
(r)

=
N
n
(r, r +dr)
V (r, r +dr)
f
n
(r)dr =
N
n
(r, r +dr)
_

0
N
n
(r, r +dr)dr
=
N
n
(r, r +dr)
C
n
g
n
(r) =
C
n

f
n
(r)
V (r,r+dr)
dr
=
C
n

f
n
(r)
S(r)
g(r) =
1
S
r

C
n
f
n
(r)
C
n
and f
n
(r) contain the structural information in g(r).
C
n
are sensitive indicators of microstructural changes.
g() = g
1
() =
C
1

f
1
()
S()
Z =
pv
k
B
T
= 1 + B
2
g() = 1 +

2D
C
1
f
1
().
C
1
=

n P
n
Hard-sphere C
n
22
0 0.2 0.4 0.6
14
14.2
14.4
14.6
14.8
15
15.2
15.4
15.6

C
1
NVE
Rnd
DRP
0 0.2 0.4 0.6
50
55
60
65
70

C
2
NVE
Rnd
Due to onset of order C
n
decreases on freezing,
F
0.494.

DRP
0.64 0.02, match with Finneys experimental data.
For perfect FCC lattice C
n
= 10 n
2
+2, Fuller(1975),
C
1
= 12, C
2
= 42, . . .
The thermodynamic solid C
n
approaches 14 near the regular close
packing, instead of 12, due to the topological instability of FCC
lattice for innitesimal perturbations, Troadec et al.(1998).
Topological instability of FCC lattice 23
The Wigner-Seitz cell of perfect FCC lattice is the rhombic dodec-
ahedron.
Vertex A formed by the intersection of 3 planes, 8 nos. (stable),
Vertex B formed by the intersection of 4 planes, 6 nos. (unstable).
On slight perturbation, a type-B vertex gets destroyed and an addi-
tional face can form instead.
Topological instability 24
1
3
4
2
5
6
1 1.5 2 2.5
0
1
2
3
4
5
r/
g
n
(
r
)
g
g1
g2
There are equal chances for an additional face to form between the
pairs (1,6), (2,4) and (3,5). Thus C
1
=12+No. of type-B vertices
Prob of forming an additional face at a type-B vertex=12+6
1
3
=14.
Few second neighbors get promoted as rst neighbors.
Due to the topological instability, polyhedra with faces 12 to 18
coexist, with the mean at 14, even near regular close packed limit.
Thermodynamic consistency 25
Z
HS
Nconf C
1
f
1
() Z
vor
0.68 36.34 256 1000 14.0252 15.00 36.07
500 512 14.0260 15.13 36.37
864 297 14.0255 15.09 36.27
1372 187 14.0249 15.20 36.53
0.72 108.05 256 1000 14.0083 46.23 108.94
500 512 14.0080 46.15 108.74
864 297 14.0083 46.29 109.08
1372 187 14.0085 46.63 109.86
Young and Alder(1979): Z
HS
= 3/+2.566+0.551.19
2
+5.95
3
,
where = (v v
c
)/v
c
= (1 y)/y, is the dimensionless excess free-
volume.
Z
vor
= 1 +

2D
C
1
f
1
().
Hard-sphere P
n
26
0 0.2 0.4 0.6
10
2
10
1
10
0

P
n
n=12
n=13
n=14
n=15
0 0.2 0.4 0.6
10
5
10
4
10
3
10
2
10
1
10
0

P
n
n=11
n=16
n=17
n=18
n=19
Due to the topological instability, polyhedra with faces 12 to 18
coexist, with the mean at 14, even near regular close packed limit.
Eective hard-sphere diameter 27
0 0.2 0.4 0.6
14
14.2
14.4
14.6
14.8
15
15.2
15.4
15.6

C
1
NVE
Rnd
DRP
Boltzmann: The distance of closest approach in particle trajectories.
Radial distribution function or its Fourier transform of soft uids can
be matched with that of HS at some diameter, Kirkwood (1942),
Verlet(1968). The notion of EHSD is useful in correlating soft po-
tential equilibrium and transport properties with the hard uid.
The integral equation approaches due to Barker and Henderson (1976),
Chandler, Weeks and Andersen (1983) and its modication by Lado
(1984), integrate the repulsive part of the LJ potential with dier-
ent criteria yielding dierent expressions for the EHSDs, results in
Ben-Amotz and Herschbach (1990).
By the equality of a soft potential C
1
with that of the hard-sphere
C
1
we estimate the EHSD.
EHSD of LJ uid 28
LJ state

values from theoretical models Voronoi analysis

T

BH WCA LWCA C
1

0.8230 0.8010 1.0226 1.0193 1.0169 14.55 1.0295

1.0649 0.7000 1.0134 1.0113 1.0090 14.77 1.0246
2.7584 0.7195 0.9742 0.9718 0.9686 14.91 0.9735
3.2617 0.9200 0.9666 0.9600 0.9558 14.70 0.9540

LJ
(r) = 4
LJ
[(
LJ
/r)
12
(
LJ
/r)
6
],
T

= k
B
T/
LJ
,

=
3
LJ
,

= /
LJ
,

= (6 //

)
1/3
.
EHSD predicted from C
1
show less than 2% deviation from the BH,
WCA and LWCA models. This shows the validity of EHSD concept
and our computational procedure.
While Boltzmanns notion was based on trajectories, ours is based
on neighbor distribution.
Summary: Neighbor statistics 29
We have shown that the information contained in g(r) is
partitioned into the sets C
n
and f
n
(r), and C
1
=

nP
n
.
We report the C
n
and P
n
for thermodynamic and random
hard-sphere structures. They are sensitive microstruc-
tural indicators.
Due to the topological instability of FCC lattice, even
near regular close packing C
1
does not approach 12, but
approaches 14.
Using the C
1
of Lennard-Jones uid, we are able to esti-
mate its EHSD within 2% deviation from the theoretical
predictions.
Sheared neighbor statistics and
non-equilibrium transitions
Phys. Rev. E 73, 051305 (2006).
Lees-Edwards boundary conditions 30
+U
U
+U/2
U/2
L
y
Inelastic hard-particles are the simplest model rapid granular matter.
In central box: v
x
= U
(yl
y
/2)
l
y
; =
U
l
y
Top crossing: v
x
v
x
U
Bottom crossing: v
x
v
x
+U
Top/bottom crossings inputs energy into the central box
and inelastic collisions dissipate the energy.
= 1 for elastic collisions, < 1 for inelastic collisions.
Voronoi partitioning of g(r) 31
g(r, ) =
1

n=1
_
N
n
r,
_
V
r,
=

n=1
g
n
(r, )
g
n
(r, ) =
C
n

f
n
(r, )
V
r,
dr d
=
C
n
r
f
n
(r, )
g(r, ) =
1
r

n=1
C
n
f
n
(r, ) (2D)
g(r, , ) =
1
r
2

n=1
C
n
f
n
(r, , ) (3D)
We show that the sheared structure C
n
are useful scalar mea-
sures, which are sensitive to non-equilibrium structural tran-
sitions.
FCC layers 32
Source: www.mines.edu
In FCC solids undergoing plastic deformation the (111) planes slide
past each other.
Colloidal crystals in plane Poiseuille ow have the (111) plane par-
allel to the velocity vorticity plane, Kanai et al.(2002), and have a
twinned-faulted FCC structure.
Shear hard-sphere C
n
33
0 0.2 0.4 0.6
14
14.2
14.4
14.6
14.8
15
15.2
15.4
15.6

C
1
NVE
=0.999
=0.90
=0.80
=0.70
x/
z
/

2 1 0 1 2
2
1.5
1
0.5
0
0.5
1
1.5
2
For = 0.999 0.80 shear ordering is in the range 0.52 - 0.53. For
= 0.70 shear ordering is near 0.55. The shear ordering packing
fraction in the preferred orientation shear varies in a narrow range.
Note the suppression of nucleation by homogeneous shear.
Close packed layers of hard-spheres move past each other in a zig-zag
path, causing a corresponding haze in the g(x, z) plot.
Close-packed layers sliding past each other oer lesser resistance to
shear than a disordered structure. Such a layer-wise ow causes
Shear-thinning in colloids and dense suspensions.
Possibility of shear-thickening 34
0 0.2 0.4 0.6
14
14.2
14.4
14.6
14.8
15
15.2
15.4
15.6

C
1
NVE
=0.999
=0.90
=0.80
=0.70
For = 0.999 0.80 shear ordering is in the range 0.52 - 0.53. For
= 0.70 shear ordering is near 0.55.
With a constant coecient of restitution, due to the lack on an in-
trinsic energy scale, the structures are shear-rate independent. Hence
shear-thickening can be observed only with a velocity-dependent co-
ecient of restitution.
Say at = 0.545, the shear rate is such that 0.80, the system is
ordered. At a higher shear rate say 0.70, then the system gets
disordered.
v
im
-dependent coecient of restitution 35
v
im
v
Y
, plastic deformation, 1.18 v
1/4

, where v

= v
im
/v
Y
,
Johnson (1985).

=
A
(A
4
+v

)
1/4
,
A 0.2 to 0.4, Spahn et al. (1997).
v
im
_ v
Y
, viscoelastic deformation, = 1
1
v
1/5
im
+
2
v
2/5
im

i
v
i/5
im
Schwager and Poschel(1998)
McNamara and Falcon (2005):
=
_
1 (1
Y
) v
1/5

if v
im
< v
Y
;

Y
v
1/4

if v
im
> v
Y
.
,
Current work:
=
A+B exp(C v
1/5

)
[(A+B)
4
+v

]
1/4
,
with A = 1.18, and B = 0.12, C = 0.44 for Nylon data of Labous et
al. (1996).
Shear amorphization at = 0.545, = 20 mm 36
x/
z
/

2 1 0 1 2
2
1.5
1
0.5
0
0.5
1
1.5
2
x/
z
/

2 1 0 1 2
2
1.5
1
0.5
0
0.5
1
1.5
2
= 2400 s
1
= 2500 s
1
Shear amorphization at = 0.545. 37
mm s
1
C
1
C
2
10 4800 14.0959 53.1667
4900 14.0978 53.1682
5000 14.5478 57.1050
5200 14.5705 57.2308
20 2300 14.1024 53.1617
2400 14.0959 53.1667
2500 14.5592 57.2328
3000 14.5627 57.1953
Savage and Jereys(1980) predict
c

1
for granular suspensions,
quoted in Barnes(1989).
At a given packing fraction,
c
/v
Y
is the only material dimensionless
group. Hence at shear amorphization
c
= constant.
For charge stabilized colloidal suspension,
c

2
, since the gov-
erning dimensionless group is
c

2
/(
0

2
0
).
Summary: Sheared neighbor statistics 38
The information contained in g(r) is partitioned into the
sets C
n
and f
n
(r). We report C
n
for homogeneously
sheared inelastic hard-spheres. They are sensitive indi-
cators of shear-ordering and shear-amorphization transi-
tions.
The suppression of nucleation by homogeneous shear is
evident in these statistics. The near-elastic sheared struc-
tures are identical to the thermodynamic structures, be-
low
F
.
Using velocity-dependent coecient of restitution, we
have demonstrated a non-hydrodynamic pathway to re-
alise shear-amorphization or shear-thickening. We nd
that
c
is a constant, for a given v
Y
and packing frac-
tion.
Bond-orientational analysis of
sheared microstructures
J. Chem. Phys. 124, 204508 (2006).
Global bond-orientational analysis 39
Angular orientation of each bond Y
lm
(, ), where 0 and
0 < 2. Rotationally invariant combinations are used to charac-
terize the microstructures, Steinhardt et al (1983).
Q
l
=
_
4
2 l +1
l

m=l
[Y
lm
)[
2
_
1/2
Q
6
= 0 for random structures and
Q
6
,= 0 for common crystalline structures.
Hence, Q
6
is used to locate any kind of crystallization.
0.3 0.4 0.5 0.6 0.7
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4

Q
6
TD
Rnd
=0.60
=0.70
=0.80
=0.90
=0.99
Local bond-orientational analysis 40
Q
l
1
l
2
l
3
=

m
1
+m
2
+m
3
=0
_
l
1
l
2
l
3
m
1
m
2
m
3
_
Q
l
1
m
1
Q
l
2
m
2
Q
l
3
m
3
,
Q
6
,= 0 for all crystalline structures. Third order invariants are used
for structure discrimination
Mitus et al.(1995) showed that Q
446
is useful for FCC structure
determination.
For an FCC cluster: Q
446
> Q
c
446
, Q
c
446
= 0.7 10
3
.
0 0.5 1 1.5 2 2.5 3
x 10
3
0
2500
5000
Q
446
f
(
Q
4
4
6
)
=0.49
=0.50
=0.55
=0.60
=0.65
0 0.5 1 1.5 2 2.5 3
x 10
3
0
2000
4000
Q
446
f
(
Q
4
4
6
)
=0.52
=0.55
=0.60
=0.64
TD Shear, = 0.90
Fraction of FCC clusters 41
0.3 0.4 0.5 0.6 0.7
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4

Q
6
TD
Rnd
=0.60
=0.70
=0.80
=0.90
=0.99
0.35 0.4 0.45 0.5 0.55 0.6 0.65
0
0.2
0.4
0.6
0.8
1

f
TD
Rnd
=0.60
=0.70
=0.80
=0.90
=0.99
Q
6
is high for dense sheared structures, so the system is crystallized.
But even in the dense, near-elastic limit there is only 40% FCC
clusters. This is a clear evidence of the coexistence of multiple
crystalline orders.
Body-centered tetragonal structure 42
ideal ideal shear
Martensitic transformation: rapidly quenched metals FCC-BCT
transition. When close-packed layers of spheres slide past each other,
BCT structures are formed.
Close-packed layers of spheres are stacked such that adjacent layer
spheres are above the mid-points of neighboring layer spheres. Lat-
tice ratios: a, a, c, 10 neighbors at a distance c = , 4 neighbors at
a distance a =
_
3/2, a/c =
_
3/2.
BCC-like polyhedra (8 hexagons and 6 squares) signature polyhe-
dra, useful in identifying local structures.
Shear hard-sphere P
n
43
0 0.2 0.4 0.6
55
60
65
70

C
2
NVE
=0.999
=0.90
=0.80
=0.70
0 0.2 0.4 0.6 0.8
10
3
10
2
10
1
10
0

P
n
NVE n=12
NVE n=14
LEBC n=12
LEBC n=14
The sheared solid C
n
are lower than the thermodynamic solid C
n
, this
is not to be interpreted that the sheared solid structures are compact
than the thermodynamic solid structures.
Note that P
12
drops sharply in the sheared solid structures, while
P
14
rises. These trends are unlike those in the thermodynamic solid
structures.
P
14
increases on shear, while P
n
for n = 12, 13, 15-18 decreases, due
to the formation of BCT structure.
Distribution of lattice ratios - BCT structures 44
a/c
a
/
b
1 1.1 1.2 1.3 1.4 1.5
1
1.1
1.2
1.3
1.4
1.5
a/c
a
/
b
1 1.1 1.2 1.3 1.4 1.5
1
1.1
1.2
1.3
1.4
1.5
Shear = 0.59 = 0.64
a/c =
_
3/2 1.225.
Maximum shearable limit:
max
0.64.
For
ord
< <
max
, the signature polyhedra are BCT type.
For >
max
, the signature polyhedra are FCC type.
Dense sheared structures show Martensitic signatures.
Distribution of lattice ratios - FCC structures 45
a/c
a
/
b
1 1.1 1.2 1.3 1.4 1.5
1
1.1
1.2
1.3
1.4
1.5
a/c
a
/
b
1 1.1 1.2 1.3 1.4 1.5
1
1.1
1.2
1.3
1.4
1.5
TD = 0.55 = 0.65
14-faceted polyhedra are formed by additional faces at a pair of
oppositely placed B vertices.
For >
F
, the signature polyhedra have a/c =

2 1.414.
Summary: Bond-orientational analysis 46
Global analysis: Q
6
is useful to locate any kind of crystallization.
Local analysis: Q
446
is useful to locate FCC clusters.
Dense random structures show negligible crystallization.
Even in the dense, near-elastic limit there are only about 40% FCC
clusters in sheared structures, even though Q
6
is high. This is a clear
evidence of the existence of multiple crystalline orders.
FCC: ABC, HCP: ABA. When close-packed layers slide past each
other random stacking faults are generated, FCC-to-HCP transition.
We showed the presence of HCP structure using a pair analysis (not
presented).
On shearing hard-spheres show FCC-to-BCT or the Martensitic tran-
sition. On shearing P
14
increases, with a decrease in P
n
for n = 12,
13, 15 - 18, due to the formation of BCT structure. The presence of
BCT structure is also shown using the signature polyhedra analysis.
In a nut-shell 47
Statistical geometry is the appropriate starting point to
develop structure-property correlations: e.g.
s
cell
= k D
_
f(v) log[f(v)]dv,
Z = 1 +

2D
C
1
f
1
(), C
1
=

n P
n
,
eective hard-sphere diameter.
Statistical geometrical measures are useful in character-
izing microstructures, e.g. m, C
n
, P
n
, Q
6
, Q
446
etc.
These measures are useful in locating structural transi-
tions: e.g. freezing, shear-ordering, shear-amorphization
and Martensitic transitions.
Acknowledgments 48
Prof. Kumaran, for his course Physics of Fluids, and
allowing me pursue a statistical-geometric approach.
Prof. Binny Cherayil for introducing Callen.
Prof. Anindya Chatterjee for his course on nonlinear os-
cillations.
JRD Tata Library and SERC.