Individual work: sketch the Lennard-Jones potential between two molecules.

It is known that the

interaction between a CCl4 molecule and a carbon atom is described with the Lennard-Jones parameters
/k = 95 K, and = 0.467 nm. (k is the Boltzmann constant). Find the distance at which the energy is a
minimum, which represents the most likely separation between a CCl 4 molecule and a carbon atom.
Repeat the same calculation for methane, where /k = 64 K, and = 0.36 nm.

-23
k= 1.3806503 10 J/K

Note that the potential energy is positive for r/ < 1, negative for r/ > 1, and zero when r =

Also note that the potential energy goes to zero for r/ >> 1:

12 6 1 12 1 6
lim / = lim 4 [( ) ( ) ] = 4 [( ) ( ) ] = 4[0 0] = 0
/ /

And the potential is infinite for r/ = 0:

12 6
lim / = lim 4 [( ) ( ) ] = 4[()12 ()6 ] =
/0 /0

Therefore, an initial sketch of the potential energy is given by the following figure:

Another important thing to determine when sketching a function is the maxima or minima:

12 6
4 [( ) ( ) ] = 0

12
4 [ 12 6 6 ] = 0

4[12 12 13 + 6 6 7 ] = 0

[12 12 13 + 6 6 7 ] = 0

6 6 7 = 12 12 13

6 = 2 6

Then the minimum is when

= 21/6 1.12
Note that when = 21/6 , =

In general, a LJ potential has the following shape:

1.5

0.5
u/

0
0 1 2 3 4 5
-0.5

-1

-1.5

-2
r/

For methane and carbon tetrachloride, the LJ potential is:

100
80 CCl4

60
CH4
40
20
u/kB , K

0
-20 0 0.5 1 1.5 2 2.5 3

-40
-60
-80
-100
r, nm

Notice that the depth of the potential is larger for CCl4 and that the size of the molecule is also larger as
the minimum of the potential is observed at a larger value of r.
Individual work: Obtain the analytical expression for u(z). How would you construct the potential of a
gas molecule between two solid infinite walls?

12

6

u z s 4 dxdy

r ( x , y , z ) r ( x , y , z )
2
12

6

s 0 4 r ( , , z ) r ( , , z ) dd
0

2 12 1 6 6 1
3

s 0 4 z 2 2 z 2 2 dd
0

change variables: a = z + and da = 2d

2 2

a 2
12 1 6 6 1
3

u z s 0 a
4 dda
a z2 a

12 1 6
a
da a

3
6 1
8 s 4 s 12 a 6 6 a 3 da
a
az2 a 2 a z2

a
a 5 a 2 12 z 10 2 4
4 10
6 z
4 s 12 6 4 s 4 10
5 2 a z2
s
5 2 5z 2z 4

1 1
10
4

u z 4 s
2

5 z 2 z

The potential of a molecule between two infinite flat walls separated at a distance h from each other, as
shown in the figure, is

uwalls = u(z) + u(h z)