8.

1 PHOTOELECTRON SPECTROSCOPY

In most cases of closed-shell molecules Koopmans theorem is a

reasonable approximation but N 2 (see Section 8.1.3.2b) is a notable
exception. For open-shell molecules, such as O2 and NO, the theorem
does not apply.

8.1.3 Photoelectron spectra and their interpretation

The simplest, and perhaps the most important, information derived
from photoelectron spectra is the ionization energies for valence and
core
electrons.
Before the equal
development
of photoelectron
rbital
is approximately
to the negative
of the spectroscopy
orbital energy
very
few of these
were known, especially
molecules.
Foror,
calculated
by a self-consistent
eld (SCF;for
seepolyatomic
Section 7.1.1)
method,
core
electrons
for orbital
i, ionization energies were previously unobtainable and
illustrate the extent to which core orbitals differ from the pure atomic
orbitals
pictured
in simple
theory.
Because
of the
generalvalence
validity
of Koopmans theorem for closed-shell
molecules
ionization
energies and, as we shall see, the associated vibrational structure
represent aof
vivid
illustration
the validity of quite simple-minded MO theory of valence
electrons.
Ii ei SCF
8:5
The negative sign is due to the convention that orbital energies e i are
At the
level of simple
valence theory
Koopmans
theorem seems to be
negative.
8.1.3.1
Ultraviolet
photoelectron
spectra
of
so
self-evident
as
to
be
scarcely
worth
stating.
with more
atomsFigure 8.6 The He I ultraviolet photoelectron spectrum However,
of argon. (Reproduced
accurate
theory,
this
is no
longer
so
interest
tonot
why
Infrom
the case
of atoms
UPS
is unlikely
to and
produce
is
Turner,
D. W.,
Baker,
C.,
Baker,
A.
D.great
andinformation
Brundle, attaches
C.which
R., Molecular
The
measured
ionization
energy
Ii is Wiley,
the
difference
in energy
Equation
(8.5)
is
only
approximately
true.
Photoelectron
Spectroscopy,
p. In
41,addition
John
London,
1970)
available
from
other
sources.
many
materials
have between
such lowM

and Mpressures
, but the that
approximation
arises in
equating
this with
vapour
their UPS spectra
may
be recorded
onlythe
at orbital
high
energy. Orbitals
an gases,
entirely
theoretical
their
temperatures.
The are
noble
mercury
and, concept
to some and
extent,
theenergies
alkali
8.1 we
Lowest
ionization
energies
I of
canHebe
obtained
exactly
only
by
calculation
then,
for The
a manymetals
are
exceptions
but
will
consider
here and
only
the 8.6.
spectrum
of
The
I (21.22
eV)Table
spectrum
of
argon
is shown
in
Figure
two
some noble gases
electron
onlythe
with
difculty.
energies
argon.
peaks
bothsystem,
result from
removal
of anExperimental
electron fromionization
the 3p orbital
in
The
three
most
important
factors
that
may
contribute
to
the
approximation
are
the
measurable
quantities
that
correspond
most
closely
to
the
the process:
Gas
I=eV
in
Equation
(8.5)
relate
to
the
main
deciencies
in
SCF
calculations
orbital energies.
ArKL3s 23p 6!ArKL3s 23p 58:7
2P3=2
2P1=2
and are:
1. Electron reorganization. The orbitals in Mare not quite the same as in
15.9electrons
From
the discussion
in
7.1.2.3 fewer.
we canThe
deduce
that the
M because
there Ar
isKrSection
one 15.759
electron
in state
M are,
Xe which
14.000
therefore,
are slightly
relative
to those
arising
from in
theorbitals
ground
conguration
of Ar reorganized
is 1S0.37
However,
the ground
2
2
1
214.6 3
1
12.130
thatLis:
P
and
P
,
since
1
and
S

,
giving
a
P
term,
and
J

or .
calculated
for
M,
222
1=2
3=2
conguration
of Ar gives rise to SCF
two

states,
SCF
65
Ar
are two
splitstates
by spinorbit
coupling.
Since
the unlled
3p orbital is more
eM
6eM
8:6
These
of
ii
than half-lled the multiplet is inverted, the 2P13.4
3=2 state being below
36
2
0.178
eV
of
the
two
peaks
in
Figure
8.6
reects
the spinorbit
coupling.
Electron
correlation.
Electrons
or molecule
do not The
P1=2 1
(Rule
4 on page 212).
The splitting
by in an atom
2121
process
Ar
P
ArS
is
approximately
twice
as
intense
as are
ionization
move entirely
independently
of each other but their movements
3=2
0
is due to the four-fold degeneracy of the 2P
This
state,
resulting
from
correlated.
The3 associated correlation energy
is often neglected
in
2222
3=2
Ar P1=2ArS
31
0.
1
withthe, two-fold degeneracy of the 2P1=2 state, for
22
MJ ,,compared
, SCF calculations.
1 1
The2HeRelativistic
I ultraviolet
photoelectron
spectra
of effects
Kr and of
Xerelativity
appear similar
to that
effects.
The neglect
on orbital
which
MJ
, of
. the
of ionization
Ar but
the
energy
decreases
anddefect
the spinorbit
coupling and
increases
with
energies
is another
common
of SCF calculations
is
increasing
number,
asatomic
illustrated
by the data
in Table
particularly
important
for core
orbital energies which can be very
8.1.
large.

8.1.3.2 Ultraviol