MONTE CARLO

SIMULATION to study
surface diffusion and
reaction processes on a
fractal catalyst
-Diffusion Limited
Aggregation
(DLA)
Rajarshi Guha(07302009)
Ankit Sharma (07302011)
Rahul Kumar (07302006)
M.Tech. 2nd Year
CL 676 course project
 What is a fractal
• A fractal is a shape made of parts similar
to the whole in some way. It is
characterized by self-similarity.

• Benoit Mandelbrot lists two qualities that

are frequently associated with fractals:
 Invariance under displacement:
under motion different regions of the
object must look similar to each other.

 Invariance under scaling: self-

similarity. Take a large DLA-cluster and
simplify it's contour, scale it down to the
size of a small DLA-cluster, they will look
quite similar.
 What is DLA
• Diffusion Limited Aggregation (DLA) occurs when a particle undergoes
Brownian motion until it makes contact with and sticks to a free-floating
cluster of particles.
• DLA- “a kinetic critical phenomenon” was invented by two physicists,
T.A. Witten and L.M. Sander in 1981.
• There are 3 methods of fractal growth-
1. Percolation
2. Particle-Cluster Aggregation (PCA)
3. Cluster-Cluster Aggregation (CCA)
• DLA comes under the category of PCA.
 Applications of DLA
Physical Processes:
• Electrochemical Deposition
• Viscous Fingering
• Dielectric Breakdown
• Monolayer formation on surface (Catalyst formation, carbon deposits etc.)
• Polymer generation from solution
• Protein Folding etc.
Natural Processes:
• Snow Flakes
• Lichen, Fern and Pine growth
• Coral Growth 80
• Creation of planets
100
100
• Lightning
• Corneal neovuscularization etc.
120 120
140
160 140
Real World Phenomena: 180
• Geographical boundary of a country
160
200
• Rural to urban migration and continuous growth 180
• Web page and computer game design etc.
200
-1
0
1

Simulation
Generated
Christmas Tree
Applications Continued..
Applications continued (simple computer simulations)..
 Laws of DLA
Fractal growth laws:

Power law: If N(r) denotes the number of particles within radius r

of a circle (or sphere) encircling a DLA then
d
N(r)= k r
For cluster in a plane d = dm ~ 1.71 is the Fractal dimension.

Density-Density correlation: The density-density correlation is

defined by

Where N is the number of particles and p(r)=1 when lattice node

is occupied and p(r)=0 when empty.

Power law correlation: C(r) and r in a special range (l<r< rmax )

follows

The fractal dimension is simply dm = (2 – a)

Laws of DLA
continues..
Mean square displacement (<X²(t)>)Power law:

When diffusion occurs on the ideal surface, the diffusion

follows Einstein relation given by in one dimension-

A growth process is called diffusion-limited when the

aggregate increases in size by one particle at a time rather
than by bunches.

This happens since the density of particles is low and thus

the particles do not come into contact with each other before
reaching the aggregate.

On a fractal surface Einstein relation does not hold.

A power law type correlation can be written as-

Where d w >2 is anomalous (or walk) diffusion exponent.
 DLA Characteristics
Lacunarity effect:
• Lacunarity is a counterpart to the fractal dimension, and describes the degree of gappiness
of a fractal.

• A fractal is very lacunar if its holes tend to be large.

• Recent analysis by Benoit Mandelbrot et al. of very large simulated clusters (more than
millions of particles) seem to show, that the cluster becomes more compact while growing.

Radius of Gyration :
The fractal dimension D for a cluster can be defined by the expression

where rg is the radius of gyration for the cluster and N(rg) is the total number of particles
within that cluster.
DLA Characteristics continues..

Sticking Coefficient:
S=0.05
• Stickiness describes the
probability that if a particle
strikes the cluster, what is
the chance of getting added.

• Stickiness=1 => Wandering

particle struck part of the
existing structure it always
stuck.

S=0.01
 Symmetric DLA – Simulation Results1

200

180
Iterations =10000
160

140

120

100

80

60

40

20

0
0 20 40 60 80 100 120 140 160 180 200

Number of Particles = 3789, 200 x 200 grid, Seed at the center,

Sfactor= 3.
 Simulation Continues..
1

0.95 Density-Density Correlation Function

0.9
density-density correlation

Fractal Dimension d = 2 - a
0.85

0.8

0.75
1200

0.7 1000
0 10 20 30 40 50 60 70 80 90 100
distance

mean square displacement

800

600

400

200

Brownian Motion of 100th particle

before sticking
0
0 10 20 30 40 50 60 70
time
 Symmetric DLA – Simulation Results2

200

180 Iterations =30000

160

140

120

100

80

60

40

20

0
0 20 40 60 80 100 120 140 160 180 200

Number of Particles = 21234, 200 x 200 grid, Seed at the center, Sfactor= 3.
 Simulation Continues...
1200

1000 Brownian Motion of 100th

particle before sticking
mean square displacement

800

600

400

1
200

0.99
0
0 10 20 30 40 50 60 70

density-density correlation
time
0.98

0.97

0.96

0.95

Density-Density Correlation Function 0.94

0 10 20 30 40 50 60 70 80 90 100
distance
 Asymmetric DLA – Simulation Results1

5 Seeds

Asymmetric
growth from
seeds

4 Seeds
 Asymmetric DLA-Simulation Results2
5
x 10
2.5

10000 particles 2

mean square displacement

1 1.5

-1 40 1
0 60
80
50 100 0.5

120
100
140
150 160 4 seeds 0
0 1000 2000 3000 4000 5000 6000 7000 8000
180 time
200

Brownian motion of 100th

particle
1000 particles
5
x10
3

Seed oriented 2.5

1 growth
mean square displacement
2
0.5

0
1.5
160
-0.5
150
-1 1
140
160

1 seed
130
140 0.5
120
120
100 110
0
100
8 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
time
 Analysis of asymmetric fractals generated
1

3600 particles on 200 x 200 grid 0.9

0.8

density-density correlation
1 seed
0.7

0.6

0.5
190 190

180 180 0.4

170 170
0.3
160 160

150 150 0.2

140 140

Correlation
0.1
130 1 130

120 0 120 0
0 20 40 60 80 100 120
-1
110 110 distance
200 180 160 140 100
100 120 100 80
90
100 110 120 130 140 150 160 170 180 190

Fractal Dimension = 2-0.25=1.75

Brownian motion
Of 100th particle
5
0.1 y vs. x
fit 2
x10
0

2.5 R q eanvs. t -0.1

s m
fit 1
-0.2
2
-0.3
Mean Square Displacement

ln(C(r))
-0.4
1.5
Power correlation
-0.5
law:
C(r)=1.56 x r^(-0.25)
-0.6
1
-0.7

Brownian Motion -0.8

<X²(t)>=88.13 x t^(0.87)
0.5
-0.9
1.5 2 2.5 3 3.5 4

0 dw = 2.29 ln(r)

0 1000 2000 3000 4000 5000 6000 7000 8000 9000

time
 Analysis of symmetric fractals generated
1200
200

180
1000
160

mean square displacement

140 800

120
600
100

80
Brownian motion
60
400
Of 100th particle
40 200

20

0 0
0 20 40 60 80 100 120 140 160 180 200 0 10 20 30 40 50 60 70
time
1

0
.9
density-density correlation

0
.8

0
.7

0
.6
1450 particles
Sfactor=3
Correlation
0
.5

0
.4

0
.3
0 1
0 2
0 3
0 4
0 50 6
0 7
0 8
0 9
0 1
00
d
is
tan
ce
 Analysis continues..
y vs. x
0.1
fit 1
0

-0.1
Analyzing by curve fitting we get-
-0.2
a = 0.35.
hence fractal dimension = 2-0.35
ln (C(r))

-0.3

-0.4
= 1.65
-0.5

-0.6 Power correlation law:

-0.7 C(r)=2.64 x r^(-0.35)
-0.8
2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 4.4
ln (r)

1200

1000
Mean square displacement

800

600 Mean square Displacement:

<X²(t)>=207 x t^(0.41)
400
dw = 4.88
200

0 10 20 30 40 50 60 70
time
 Simulation Procedure (Algorithm)
Symmetric DLA
• Initialize the grid and define
necessary variables (eg. Define
diffusion time, seed etc.)
Asymmetric DLA
• Initialize grid, define necessary
variables and distribute seeds
randomly.

• Release particles from the • Generate a particle within grid

periphery of the circle.
and put it in random walk until a
particle is encountered.
• Apply Brownian motion until it
finds the cluster.
• It sits beside the encountered
particle.
• Keep on tracking distance from
seed and kill particle if it goes
outside. • The process continues until
definite number of particles is
attained.
• If particle satisfies Sfactor criteria
it is allowed to proceed.

• Then particle adheres to one of

the free available sites.

• The process goes on until the grid

circumference is reached.
 Application
N2O decomposition kinetics by MC simulation (Guo et al., 1994):
2 step kinetics :

Surface coverage θ, when R1=R2

can be expressed as

Theoretically: For the 2 step reaction mechanism 2nd step

occurs on Catalyst surface. Rate constant K2 is related to speed of
surface diffusion v2D by-

Speed of surface diffusion is directly proportional to surface

diffusion coefficient.
Hence, At constant temperature K2 ∞ D. This approach gives
K2 = 0.6
 Application Continues..

Ideal surface:
Overall rate law by MC simulation
Fractal Surface:

Figure showing the DLA fractal generated

By Guo et al. (Fractal dimension 1.72)

Monte Carlo simulation generated K2 = 0.58

Theoretical K2 = 0.6
 Conclusions
• Many physiconatural processes are random and MC
DLA simulation can actually represent those
processes computationally.

• DLA fractals are recognized by their fractal

dimension and power law correlation.

• An important application of DLA is to simulate fractal

catalyst surface and thereby modifying the rate law
of surface reaction.