(
r
(
t
)
r
(
0
))
i
i
N i =1
The MSD contains information on the diffusion coefficient D,
r
MSD = r ( t ) 2 = A + 6Dt + fluctuations
This expression is called Einstein relation since it was first derived by Albert
Einstein in his Ph.D. thesis in 1905 (see note below)
The 6 in this formula becomes 4 for a two-dimensional system and 2 for a onedimensional system (see next page)
This
Time
by D.
C (x , t
t
Solution: C (x, t ) =
)=
2 C (x , t
D
x 2
x2
1
exp
Dt
4Dt
C (x , t )dx
x 2 (t )
t
= D
2 C (x , t )
dx
x 2
(t )
2 C (x , t )
2 C (x , t )
= D x
=
dx
D
x
dx
2
x
x
x
2
x 2 C (x , t )
C (x , t )
2 C (x , t )
D
dx = Dx
2D x
dx =
x
x
x
x
+
= 0 2D
= 2 DxC (x , t ) + 2 D C (x , t )dx = 2 D
+
(t )
= 2 Dt
+ A
for 1D diffusion
r
C (r , t
(rr , t ) =
1
)=
(2 Dt
)d / 2
(rr , t )
r2
exp
2 Dt
r 2C
r
r 2 (t )
t
(rr , t )d rr
2
= D
r 2
(rr , t )d rr
(t )
r
r r
r
r
r
2
= D r C ( r , t )d r = D r C ( r , t ) d r
2
r
r 2 r r
r r
r
r r r
r
2
D r C ( r , t )d r = D r C ( r , t )dS 2 D r C ( r , t )d r =
r r r
r r r
r
r
= 0 2 D ( r C ( r , t ))d r + 2 D r C ( r , t )d r =
r
r r
r
r
(
)
(
)
= 2 D r C r , t d S + 2 dD C r , t d r = 2 dD
(t )
=1
= 2 dDt
+ A
Gradient:
Laplacian:
x +
y +
z
x
y
z
r
r
=
r
r
(r)
x +
y +
z
x
y
z
2
2
2
+
+
z2
y 2
x 2
r r r
Fy
Fz
Fx
+
+
F(r)
z
y
x
) ((
r
r r r
r r r r
( r )F( r ) = ( r ) F( r ) +
r r r r
F ( r )d r =
r r
r
r
(r) F(r)
r r r
F ( r )d S
lim
f (x )
= lim
df dx
d equilibrium
interatomic
distance
d
50
Atomic paths of two atoms in FCC lattice at temperature below the melting
temperature. Figures are from MD simulations by E. H. Brandt, J. Phys:
Condens. Matter 1, 10002-10014 (1989).
Can we use the Einstein relation to calculate the Diffusion coefficient from these
atomic trajectories?
d equilibrium
interatomic
distance
Atomic paths of two atoms in amorphous and liquid systems. Figures are from
molecular dynamics simulations by E. H. Brandt, J. Phys: Condens. Matter 1,
10002-10014 (1989). Two longest atomic paths for each simulation are shown.
Can we use the Einstein relation to calculate the Diffusion coefficient from these
atomic trajectories?
University of Virginia, MSE 4270/6270: Introduction to Atomistic Simulations, Leonid Zhigilei
1
D=
3
r
r
1
v ( t ) v ( 0 ) dt =
3N
i =1
r
r
( v i ( t ) v i ( 0 ))dt
To get most from your MD trajectories you can use averaging over starting
times.
1.
2.
3.
4.
The plots are from the computer simulation by T. Kwok, P. S. Ho, and S. Yip. Initial atomic
positions are shown by the circles, trajectories of atoms are shown by lines. We can see the
difference between atomic mobility in the bulk crystal and in the grain boundary region.
University of Virginia, MSE 4270/6270: Introduction to Atomistic Simulations, Leonid Zhigilei
D(T ) = D 0 exp a
k
T
B
Note the deviation of the diffusivities from the Arrhenius behavior at high
temperatures, when kT becomes comparable or larger than the activation
energies. This indicates a change in the mechanism of atomic mobility (change
in Ea, collective motions..?).
University of Virginia, MSE 4270/6270: Introduction to Atomistic Simulations, Leonid Zhigilei
G.B.
=D
G.B.
0
G.B.
exp
k BT
with the activation energy for grain boundary diffusion significantly lower than
the one for the bulk. However, the effective cross-sectional area of the
boundaries is only a small fraction of the total area of the bulk (an effective
thickness of a grain boundary is ~0.5 nm). The grain boundary diffusion is less
sensitive to the temperature change becomes important at low T.
EM
R B = R 0 exp
kT
DB ~ a 2 NVR B
T. Kwok, P. S. Ho, and S. Yip, MD studies of grainboundary diffusion, Phys. Rev. B 29, 5354 (1984).