3 Dissociation energies of

diatomic molecules

3.1 I N T ROD U C T ION

The term dissociation energy may be appreciated by reference to potential

energy internuclear distance curves. At about 0 K all molecules have no ro-
tational energy but are merely vibrating with their zero-point energy. Thus,
diatomic molecules are in the v = 0 vibrational level. The energy required to
separate the stable molecule A B initially in the v = 0 level into two unexcited
atoms A and B, that is:
A-B-+A+B

is known as the dissociation energy (D), its value being represented in Fig. 3.1.
Another symbol which is often used by spectroscopists is De where:

D" = D + C(O) (3.1)

C(O) = Ev=o/hc and is the value of the vibrational energy in the v = 0 level. As
C(O) is in cm -I units, then De and D would also be in these units.
In the literature dissociation energy values are mainly to be found quoted in
kcal mol-I, cm -I, or electron-volts (eV). The SI unit system employs kJ mor l .
It is useful to have the following conversion factors: 1 cm- I = 1.23981 x
1O-4 eV/molecule = 0.002859 kcal mol-I = 0.Q11962 kJ mol- J •
The value of the dissociation energy can be found by thermochemical
methods. However, its value differs very slightly from the corresponding one
CD) obtained from spectroscopic data since the latter is calculated for 0 K while
the former is for 298 K. It is, however, possible to convert by making certain
assumptions from one to the other r 3 .1] .
Infrared spectroscopy can be used to determine D and De for the ground state
of the molecule, while electronic spectra can be used to determine D and De not

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© Chapman and Hall Ltd 1976
Spectroscopy Volume Three

only for the ground state of the molecule but also for some of the excited states
as well.
In the electronic spectra approach for the determination of the dissociation
energy at least one of the products of dissociation is frequently in an excited
state, and in some cases both atoms are excited. In some instances the dis-
sociation may even take place into ions.

A+8

r----------------
D

Internuclear distance-

Fig. 3.1 Potential energy curve and the representation of thermal dissociation D
and spectroscopic dissociation energy De

In order to determine the dissociation energy from spectroscopic data it is

necessary either (1) to determine the lowest absorption frequency which will
produce dissociation of the molecule, and to identify the electronic state of the
dissociation products, or (2) to determine the energy values of as many
vibrational levels for the electronic state whose dissociation energy is required.
Electronic spectra may proceed by either (1) or (2) whereas the infrared
approach cannot be used to study actual dissociation and is therefore restricted
to (2).
The aim in this chapter is to give a simple account of dissociation energies of
diatomic molecules. For a more rigorous and fuller treatment the book by
Caydon [3. J 1 should be consulted.

3.2 EVALUATION OF D BY BAND CONVERGENCE METHOD

In Fig. 3.2 five of the potential energy curves are given for the oxygen molecule.
When dissociation of the molecule takes place from any of the four lowest elec-
tronic states given in Fig. 3.2 it leads to two oxygen atoms each in a 3p state,
that is:

104