Notes 9: The hydrogen molecule

We can apply the techniques used to understand covalent bonding in the hydrogen molecular ion to the
hydrogen molecule, H2. Again, the Born-Oppenheimer approximation will be used, and the trial wave
function will created using the hydrogen atom ground state wave function. If the protons were far apart,
i.e. a separation of many Bohr radii, we would expect, in the ground state, one electron to be attached to
one of the protons, and the other electron to be attached to the other proton. In this case, we might
consider a trial wave function

 r1, r2   0 r1 

(9.1)
0 r2,

where r1 and r2’ are as shown in the figure,

-e

r12
r1 r1’
-e
r2 r2’

+e R +e

and

1
 0 r  er a . (9.2)
a3


A useful concept to visualize bonding is the probability density, n(r), which is the probability per unit
volume of finding either electron in a small volume d3r around a point r. The probability density is found
by performing integrals for each electron of the wave function over all space for all the other electrons,
i.e. for two electrons with normalized wave function  r1, r2 ,
n r    r, r 2 2
3r ,  d 3r   r , r  d (9.3)
 2 2  1 1

For the two hydrogen atom wave function in equation (9.1), we have
n r    r  r  2 d 3r 2
      r  r d 3r
 0 1
2
0 2
2
2  0 1 0 2 1 (9.4)
  r    r ,
0 0

1
which is shown in the figure below:

2
 0.32

1.0 0.29

0.26

0.5 0.23

0.20

0.0 0.17

0.13

-0.5 0.10

0.07

0.04
-1.0
0.01
-2 -1 0 1 2
x

If the protons are close together, we might expect that the electrons would be shared by the
protons, as was the case for the H2+ molecule. Trial wave functions that are symmetric or antisymmetric
under electron exchange are

   r1, r2   A  0  r1  0  r2   0

(9.5)
 r1 0  r2  ,

where the normalization factor A involves the same exchange integral found for the H2+ molecule

A  1 . (9.6)
2 1 I 2 

Note that the wave function in equation (9.5) is also symmetric or antisymmetric under proton exchange.
The probability density function is

n  r   2 A2  02  r   2I 0  r  0  r   (9.7)

 02  r    ,

where r and r are the distances of a point with position vector r from the two protons. The figure on the
left (right) shows the probability density function for the + (-) sign trial wave function. We see that the
probability of finding the electron between the protons is greater for the + sign trial wave function. The
electrons screen the protons from each other, which allows the possibility of a covalent bond.
x
0.8 0.8 0.30

0.6 0.6
0.27

0.4 0.4

0.24
0.2 0.2

0.0 0.0 0.21

-0.2 -0.2
0.18
-0.4 -0.4

0.15
-0.6 -0.6

-0.8 -0.8 0.12

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
x
0.09

3
0.06

0.03

0.00
0.50

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00

4
 The Hamiltonian for the electrons in the H2 molecule is

2 e2  1
1 2 e 2  1 1  e2 1
   
2
2 .
H   2m 1  4  r  r   2m 2  4 r r 4 r (9.8)
e 0 1 1  e 0  2 2  0 12

The expectation values of all terms, except the last term for the electron interaction, can be evaluated
using the same integrals found for the H2+ molecular ion. The remaining term

e2
Vee   1 , (9.9)

r12
40

involves the integrals

2 2
D   r    r   d 3r d 3r ,
a
r12
2  0 1 0
a 2 1 2
(9.10)
X    r  r  r  r d 3r d 3r .
2  0 1 0 1
r1
0 2 0 2 1 2

After much work, these integrals can be shown to be

1  1 11 3 1 
D2    e2    8  4  6  2

 5 23 3 
X  e2     2 1 3 (9.11)
2   
8 20 5 15 

 
61  I   I 
2

 I 2   ln   2 E 2     E 4  ,
5  I
1 1
I 
where  is Euler’s constant, E1(x) is an exponential integral function

et
E1  x   dt, (9.12)

and  t 1
 
x
I2
  e 1    (9.13)
.
 
3
5
  
Adding all terms together, including the potential energy of the proton interaction, we get
E  
 1 2D  D2  2IX  X 2  (9.14)
   
. 1 I 2
 2E1 1
  
The energy curves are shown below.

6
 0

-1

E/|

-2

0 1 2 3 4 5 6

The symmetric trial function energy has a minimum of 2.232 E1 at R = 1.64 a. Hence the hydrogen
molecule is bound by at least 3.15 eV (the experimental value for the dissociation energy of H 2 is 4.52
eV).
The adopted trial function misses out a lot of the ‘physics’ of the particle interactions. For
example, we found earlier that two widely separated hydrogen atoms had a weak mutual attraction
described by an R-6 potential energy. This is not found in the above analysis. Adding terms to the trial
function similar to those in the Hylleraas wave function resolves these deficiencies due to neglect of
electron correlation1.

1
E.g. James, H. M., Coolidge, A. S. 1933 J. Ch. Ph., 1, 825J