Kinetic Monte Carlo

Triangular lattice

Diffusion
D = DJ
Thermodynamic
factor

Self Diffusion

Coefficient

N
kB T
=
=
ln x
N2 N

1
DJ =
(2d)t

N r 2
1
R i (t)

N
i=1

Diffusion
r
R j (t)

r
R i (t)

1
DJ =
(2d)t

N r 2
1
R i (t)

N
i=1

1
1
D* =
(2d)t N

i=1

r 2
R i (t)

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(E b k B T )

Standard Monte Carlo to study

diffusion

Pick an atom at random

Pick a hop direction
Calculate exp(E b k B T )
If ( exp(E b k B T ) >
random number) do the hop

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).

For each potential hop i,

calculate the hop rate

E
i
Wi = * exp

kB T

For each potential hop i,

calculate the hop rate

E
i
Wi = * exp

kB T
Then randomly choose a hop k, with probability

Wk

For each potential hop i,

calculate the hop rate

E
i
Wi = * exp

kB T
Then randomly choose a hop k, with probability

1 = random number

Wk

For each potential hop i,

calculate the hop rate

E
i
Wi = * exp

kB T
Then randomly choose a hop k, with probability

1 = random number
k1

N hops

W < W W
i

i=1

i= 0

Wk

W =

i= 0

Then randomly choose a hop k, with probability

1
k1

= random number
N hops

W < W W
i

i=1

Wk

W =

i= 0

i= 0

Time
After hop k we need to update the time
2

= random number

1
t = log 2
W

Two independent stochastic

variables:
the hop k and the waiting time t

k1

W < W W
i

i=1

N hops

W=

i= 0

E
i
Wi = * exp

kB T

1
t = log 2
W

i= 0

Kinetic Monte Carlo

Hop every time

Consider all possible hops simultaneously
Pick hop according its relative probability
Update the time such that t on average
equals the time that we would have waited
in standard Monte Carlo
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
r
E( ) =

N latticesites

l=1

1
1

V
+
V

+
V

+
V

po int l
NNpair l
i
NNNpair l
j
o
2
2

i=
NNpairs
j=
NNNpairs

Activation barrier

E kra

1
= E activated state (E1 + E 2 )
2

E barrier = E kra

1
+ E final E initial
2

Thermodynamics
D = DJ

N
kB T
=
=
ln x
N2 N

Kinetics
D = DJ
DJ =

1
(2d)t

N r 2
1
R i (t)

N
i=1