8.

1 PHOTOELECTRON SPECTROSCOPY

8.12 The He I ultraviolet photoelectron spectrum of benzene.

(Reproduced from Karlsson, L., Mattsson, L., Jadrny, R., Bergmark, T. and
Siegbahn, K., Physica Scripta, 14, 230, 1976)
Figure

degeneracy. The only relatively simple structure is observed in the

seventh system in which an electron is removed from the 3a1g orbital.
There is a long progression in n 1, the a1g ring-breathing vibration (see
Figure 6.13f ) consistent with the electron coming from a s CC bonding
orbital.

8.1.3.3 X-ray photoelectron spectra of

gases
We have seen above how X-ray photons may eject an electron from the
core orbitals of an atom, whether it is free or part of a molecule. So far,
in all aspects of valence theory of molecules that we have considered,
the core electrons have been assumed to be in orbitals which are
unchanged from the AOs of the corresponding atoms. XPS demonstrates
that
this
is almost,
but notinquite,
true.
This
point
is illustrated
Figure
8.13 which shows the X-ray photoelectron
2 spectrum
: 1 mixture
of aof CO and CO2 gases obtained with MgKa (1253.7 eV)
source radiation. The ionization energy for removal of an electron from
the 1s orbital on a carbon atom, referred to as the C 1s ionization
energy, is 295.8 eV in CO and 297.8 eV in CO 2, these being quite
comfortably resolved. The O 1s ionization energy is 541.1 eV in CO and
539.8 eV in CO2, which are also resolved.
Vibrational structure is, at best, only partially resolved. The structure in
the rst and second systems is complex which could be due, in part, to
there being a JahnTeller effect in each of them. Such an effect may
arise when a molecule is in an orbitally degenerate E (or T ) state. The
JahnTeller effect involves a distortion of the molecule in order to
destroy the