8.

1 PHOTOELECTRON SPECTROSCOPY

several overlapping progressions. These have been attributed to the

3 3
S , D,1S and 3Sstates, as indicated on the spectrum (the last two states
are almost degenerate). The other two band systems are too weak to be
Finally, removal of an electron from the s2p orbital gives the
observed.
conguration
1
4
NO...s2p p2p p
1

*2p
from which two states arise (see Equation 7.75), 1P and 3P. We might
expect long progressions associated with these two states because of the
apparent bonding character of the s2p orbital. However, the photoelectron
spectrum of nitrogen in Figure 8.9 shows that the corresponding orbital is
almost non-bonding in character, contrary to expectation from a simple
molecular orbital picture. The very short progressions associated with the

1
P and 3P states of NO , shown in the spectrum above, indicate a similar
non-bonding character of this orbital in NO also.

8.1.3.2(d) Water The ground MO conguration of H2O is (see Section

7.3.1.1 and Figure 7.31)
2

...2a1 1b2 3a1 1b1 8:8

1
and the HOH angle in ~
the
A

B1
ground ground
Removal
of an electron
theof1b1 orbital, which, as Figure 7.31 shows,
2
state from
is state
A
1
~
any
particular
bond
angle,
to
give
the
(ReproducedwithpermissionfromTurner,D.W.,Baker,C.,Baker,A.D.andBrundl
does not favour
104.5. H2Osho
state of
e,C.R.,MolecularPhotoelectronSpectroscopy,p.53,JohnWiley,London,1970)
The He Iuld not
H2Osinc
ultraviolaffect
e,isas
~2Bin
angle
110.5
in the
Since
the vacancy
orbital behaves, in this respect, like a single
et
the
1 the p2p
Figure
1
1
electron, the states
arising
are
the same as those from p2p p*2p ,
photoele
state, a
angle
7.31
2
and
P1=2
isofcan
the
inelectrons
energy
and,
therefore,
the
ground
state.
Removal
anlower
electron
from
3aorbitals.
inEquation
H2O should
to a large
since
we
ignore
inthe
lled
(7.77),lead
dropping
ctron
1 MO
rather
very
shows,
~ g and
in increase
the
the
u subscripts
for
a
heteronuclear
diatomic
molecule,
gives
in angle
spectru
larger
much.
this
m is
change
Both n1,
orbital
p S
SD
Removal of an electron
frompthe
outermost,
p*2p, orbital results in the
shown
from
the
theconguration
favours
in Figuresymmet
ground
a linear
2
...s2p
Since
there are two
electrons
(actually
a4p
vacancy and an electron) to
p2p
8.11.
state
of NO ric
molecul
0
consider there are three singlet and three
triplet states
*2p
H2 O
stretchin

e. The
1
which gives rise than
to just one state,
S , the
ground
state of NO. Since the
1S
3
1
3
1
g,
and
observat
; S ; S; S; D; 3 D
orbital from which
the electron
has
been
removed
is antibonding, we
might
n2, the
ion of a
would
expect
a
shortening
of
the
bond
and
a
reasonably
long vibrational
have
arising.
angle
long
progression.
The
He
I
photoelectron
spectrum
below
shows
thatsix
this
is the
been
All
ionisation
processes
are
allowed
so we
mightgives
expect
from
the
bending,
progress
Removal
of an
electron
from
the p2p
orbital
the
case.
The
ionisation
energy
is
9.26
eV.
expecte
ground
state
of
NO.
All
of
them
would
be
expected
to
show
fairly
long
vibratio
ion in
conguration
d.
vibrational
progressions
because
showthe
electron
is ejected from a p2p
the
2
3
ns
NO
...s2p
p2p
p
bonding
a lengthening
of the bond. Ignoring the two
bendingorbital resulting in only
1
*2p spectrum in the 1520 eV region is
short
very
intense peaks, the photoelectron
vibratio
progress
very
showing
n n2complex
,
ions.
shown
The
in Figure
high8.11, is
resolutio
consiste
n
nt with
emissio
the
n
increase
spectru
of the
m of
angle to
180 (see
H2Ohas
Table
shown
7.8).
that the
1

The third band system, involving the removal of an electron from the 1b2 orbital, is
vibrationally complex, consistent with the orbital being strongly bonding and favourin