The diatomic molecule

In a diatomic molecule, the energy may be considered as being made up

of five independent contributions:
1. The translational motion of the molecule as a whole
2. The rotational motion of the molecule as a whole
3. The vibrational motion of the two atoms along the axis of the molecule
4. The motion of the electrons around the nuclei
5. The nuclear spin

Its partition function is Z  Zt Z r Zv Ze Z n

Where: Zt is the translational partition function
Zr is the rotational partition function
Zv is the vibrational partition function
Ze is the electronic partition function
Zn is nuclear spin partition function
Possible motions of a diatomic molecule

(a) Translational motion of the

center of mass,

(b) rotational motion about the

various axes,

(c) Vibrational motion along the

molecular axis.
The translational motion of a diatomic molecule

Translational motion of the center of mass,

m = m1 +m2

2 2
h 
j  n j
2
V 3
8m
   2 m k T 
32
n 2j  nx2  n y2  nz2 Zt  V  
 h 
2
nx, ny, and nz are all positive

px2  p y2  pz2 p2
 
2m 2m
 The rotational motion of a diatomic molecule

Rotational motion about the various axes

I : the moment of inertia of the molecule
about an axis through its center of gravity.
j : quantum number of total angular
momentum.
mj : magnetic quantum number.
For each value of j, mj take any of values
h2 between j, j+1, .., 0, ......j. Thus, there are
 j  j  j  1
8 2 I (2j +1) states for each energy level .


Z r   2 j  1 e
 j / kT
I    02
j 0

h2
Z r   2 j  1 e
mm  j  j 1 / kT
 1 2 ; 
m1  m2 j 0 8 2 I
 The vibrational motion of the two atoms
along the axis of the molecule


 n  12 h 
Z  exp  k T 
n 0  


  1  x  ; x  1
1
 1
n
x
  n  h n 0

 2 1
 h / kT 
 nh / kT
Z e 2  e
n 0
1 k
v
2 
1  e 
1
 h / kT
 h / kT 1
Zv  e 2
m1m2

m1  m2
 The motion of the electrons around the nuclei
If e1, e2, e3 are the energies required to excite an electron from
the ground state to the first exiced state, the second exiced state,
the third excited state of the molecule then the partition function
will be:
e1 / kT e 2 / kT
Ze  g0  g1e  g 2e  ....
g0 is the degeneracy of the ground state
g1 is the degeneracy of the first exiced state
g2 is the degeneracy of the second excited state
The electronic partition function can usually be represented by
the first two terms.
e1, e2 are very much larger than the thermal energy kT ,
except at very high temperature. It is generally possible to write:
e1 / kT
Ze  g0  g1e
The complete partition function of a diatomic molecule

Z  Zt Z r Zv Ze Z n
 2 m k T 
32

Zt  V  
 h 
2


h2
Z r   2 j  1 e  j  j 1 / kT ; 
j 0 8 2 I

1  e 
1
 h / kT
 h / kT 1
Zv  e 2

e1 / kT
Ze  g0  g1e
Zn
 Energy of the gas of N diatomic molecules

  ln Z t  ln Z r  ln Z v  ln Z e  ln Z n 
U  NkT  2
    
  T  T T T T 
2   ln Z t  ln Z r  ln Z v  ln Z e 
U  NkT      0
 T T T T 
3     
 2 j  1e
ln  j  j 1 / kT
 kT  kT  
2

 2 T  j 0  
UN
 e1 kT 
hv 1  1  g1 e1 e 
 
  2 e hv kT  1  g 0  g1e e1 kT 
 the electronic partition function
Ze   g je
 j / kT

j is the energy of level j, gj is the degeneracy of that level.

For Hydrogen atom, the energy of a state :
 e4  1   1
n  2 2 1  2   R1  2 
8 0 h  n   n 
 is the reduced mass of the atom, e is the electric charge of the electron,
R is the Rydberg constant = 13.6 eV
It is taken that the ground state is a reference level for the energy at n =1.
The principal quantum number n can take any positive values, there is an
infinite number of excited states.
If electron spin is not considered, the degeneracy of each level is simply n 2.

For n = 1, l = 0, ml = 0
For n = 2, l = 0, ml = 0
l = 1, ml = -1, 0, 1
For n = 3, l = 0, ml = 0
l = 1, ml = -1, 0, 1
l = 2, ml = -2, -1, 0, 1, 2

Z e   n 2e n kT
;1  0,2  10.20 eV,3  12.09 eV
n 1

kT = 2.569 x 10-2 eV for T= 298 K (i.e. 25oC)

13.6/(2.569 x 10-2) = 529; 10.2/(2.569 x 10-2) = 397;

Ze  1  e 529
 n
n2
2 This series diverges, a divergent series

m
1 3 1 2 1

n 1
n 2

3
m  m  m
2 6
 
Ze  1  e 529
n
n2
2

It is estimated the contribution of the excited levels for 105 terms.

 
1 
105
Z e  1  10  230  n 2  1  10  230  10 5  ...  1  10  215
3

n2 3 