T.

JOSPHIN ANTO MONISHA

II-MSc.CHEMISTRY
 Ultra violet photo electron spectroscopy is a
technique in which an ultra violet radiation is
used to eject the valence electron of an atom or
a molecule.
 The binding energy of electrons in the valence
level of an atom is nearly 5-30 eV.
 It is possible to eject electrons with the x-ray
radiation but the higher resolution is obtained
with ultra violet radiation.
 The fine structure of band can only be observed at
higher resolution which results from transitions to
more than one vibrational level in the ion.
 Transitions originate from v=0 state in a neutral
molecule to one of the vibrational state of the ion
results a series of approximately equally spaced
bands in the spectrum.
 These transitions are governed by franck condon
principle.
 The intensity will be high where the bond length of
the ion is closest to that in the neutral species.
 The bond length and the other properties in turn
depend on what sort of electron is ionized.
 If an non bonding orbital is removed, there is
virtually no change in the bond strength or length
The bond becomes stronger; the bondlength becomes
shorter.
 The potential well for the ion is rather deeper and
narrower than that of the molecule,and the vibrational
frequency increases; hence there is increase in the bond
length.
 The bond becomes weaker and longer bond length.
 The decrease in bond strength results in a wider and
shallower potential well, with a lower frequency than that
of the neutral molecule.
CO has totally 10 valence electrons(6 from O and 4 from
C ) the outer 8 of which occupy the molecular orbitals
2σ(2)2π(4)2n(2) ; n represents the non bonding
electron.

 The 14eV band has no fine structure –represents the

removal of an electron from the non bonding orbital.
 The band at 16.5eV with its associated fine structure
arises from 2pπ bonding orbital which is high in energy
than 2sσ the latter gives rise to 19.7eV.
 The vibrational space is observed to be 1549cmˉ1for the
16.5eV band and the 1706cmˉ1 for the 19.7 eV band;
both of these values are significantly lower than that of
the fundamental frequency of the free molecule
indicating the removal electron from the bonding orbital.
 The spacing of the lines for the 14.0eV band is about
2200cmˉ1, which indicates the removal of electron from
the non bonding orbital.
Two effects:
i) spin orbit coupling may take place and results
in the additional splitting of bands,
ii) if an electron is removed from degenerate
level the resulting ion may initially be in a
degenerate level and subsequent distortion of
the ion may lead to the removal of the
degeneracy and the splitting is known as
Renner Teller effect for linear molecule and
Jahn Teller effect for non linear molecule.
 It is a technique in which x-ray radiation is used
to eject the core electrons.
 Although such electrons play a little role in the
chemical bonding different chemical
environment can induce the small changes in
their binding energies.
 During the bond formation there will be change
in the distribution of the electrons and hence
produces effective changes in the nuclear
charge bound by the electrons.
 EXAMPLE:1 C-F
 The highly electronegative F attracts the
electrons and so reduces the electron density
around the carbon nucleus ; the carbon is less
shielded than in the free state and is nuclear
charge is increased.
 The core carbon electrons experience an
increased nuclear force and so have a higher
binding energy.
 This phenomenon is known as the chemical
shift.
 Example 2: N₂O
 It is a linear molecule N-N-O and so the central
nitrogen experiences a greater reduction of
electron density and hence more strongly
bound core electrons .
 The central atom is assigned to be at412.6eV
peak and the end atom to the 408.7eV peak.
 In general, the XPES splittings are usually so
small that they cannot be resolved and appear
as slightly broadening of the bands
Fundamental of molecular spetroscopy
Colin N. Banwell and Elaine M. Mc cash
Fourth Edition
Tata Mc Graw Hill Edition.
Pg No. 194-197.
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