Kinetic Monte Carlo

Triangular lattice
Diffusion

D=O D
J

D
J
=
1
2d
( )
t
1
N
AR
i
t
( )
i=1
N

|
\


|
.
|
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2

O=
c

k
B
T
|
\

|
.
|
c ln x
=
N
N
2
N
2
Thermodynamic
factor
Self Diffusion
Coefficient

AR
i
t
( )

AR
j
t
( )

D
J
=
1
2d
( )
t
1
N
AR
i
t
( )
i=1
N

|
\


|
.
|
|
2
Diffusion

D* =
1
2d
( )
t
1
N
AR
i
t
( )
2
i=1
N

Standard Monte Carlo to study

diffusion
Pick an atom at random

Standard Monte Carlo to study
diffusion
Pick an atom at random
Pick a hop direction

Standard Monte Carlo to study
diffusion
Pick an atom at random
Pick a hop direction
Calculate


exp AE
b
k
B
T
( )
Standard Monte Carlo to study
diffusion
Pick an atom at random
Pick a hop direction
Calculate
If ( >
random number) do the hop

exp AE
b
k
B
T
( )

exp AE
b
k
B
T
( )
Kinetic Monte Carlo
Consider all hops simultaneously
A. B. Bortz, M. H. Kalos, J. L. Lebowitz, J. Comput Phys, 17, 10 (1975).
F. M. Bulnes, V. D. Pereyra, J. L. Riccardo, Phys. Rev. E, 58, 86 (1998).

W
i
= v * exp
AE
i
k
B
T
|
\

|
.
|
For each potential hop i,
calculate the hop rate

W
i
= v * exp
AE
i
k
B
T
|
\

|
.
|
For each potential hop i,
calculate the hop rate
Then randomly choose a hop k, with probability

W
k

W
i
= v * exp
AE
i
k
B
T
|
\

|
.
|
For each potential hop i,
calculate the hop rate
Then randomly choose a hop k, with probability

W
k
= random number

1

W
i
= v * exp
AE
i
k
B
T
|
\

|
.
|
For each potential hop i,
calculate the hop rate
Then randomly choose a hop k, with probability

W
k
= random number

1

W
i
i=1
k1

<
1
W s W
i
i= 0
k

W = W
i
i=0
N
hops

Then randomly choose a hop k, with probability

W
k
= random number

1

W
i
i=1
k1

<
1
W s W
i
i= 0
k

W = W
i
i=0
N
hops

Time
After hop k we need to update the time
= random number

2

At =
1
W
log
2
Two independent stochastic
variables:
the hop k and the waiting time

W
i
i=1
k1

<
1
W s W
i
i= 0
k

At =
1
W
log
2

W = W
i
i=0
N
hops

W
i
= v * exp
AE
i
k
B
T
|
\

|
.
|

At
Kinetic Monte Carlo
Hop every time
Consider all possible hops simultaneously
Pick hop according its relative probability
Update the time such that on average
equals the time that we would have waited
in standard Monte Carlo

At
A. B. Bortz, M. H. Kalos, J. L. Lebowitz, J. Comput Phys, 17, 10 (1975).
F. M. Bulnes, V. D. Pereyra, J. L. Riccardo, Phys. Rev. E, 58, 86 (1998).
Triangular 2-d lattice, 2NN
pair interactions

E o ( )= V
o
+V
point
o
l
+
1
2
V
NNpair
o
l
o
i
i=NNpairs

+
1
2
V
NNNpair
o
l
o
j
j=NNNpairs

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\



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l=1
N
lat ticesit es

Activation barrier

AE
kra
= E
activatedstate

1
2
E
1
+E
2
( )

AE
barrier
= AE
kra
+
1
2
E
final
E
initial
( )
Thermodynamics

O=
c

k
B
T
|
\

|
.
|
c ln x
=
N
N
2
N
2

D=O D
J
Kinetics

D=O D
J

D
J
=
1
2d
( )
t
1
N
AR
i
t
( )
i=1
N

|
\


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2