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The electronic structures of homonuclear

diatomic molecules
For bonds between atoms of a given pair of elements:

1. The greater the bond order, the shorter the bond.

2. The greater the bond order, the greater the bond

Photoelectron spectroscopy

Photoelectron spectroscopy (PES) measures

the ionization energies of molecules when electrons are
ejected from different orbitals by absorption of a photon
of the proper energy, and uses the information to
infer the energies of molecular orbitals.
Fig. 34 An incoming photon carries an energy hν ; an energy
Ii is needed to remove an electron from an orbital i, and the
difference appears as the kinetic energy of the electron.
hν = 1/2 mev2 + Ii

A photoelectron spectrometer consists of a source of

ionizing radiation
Type of photoelectron spectrometer

1. UPS
2. XPS

1 eV = 8065.5 cm−1
1 nm = 10-9 m = 10-7 cm
Illustration Interpreting a photoelectron spectrum
Photoelectrons ejected from N2 with He(I) radiation had kinetic energies of
5.63 eV (1 eV = 8065.5 cm−1). Helium(I) radiation of wavelength 58.43 nm
has wavenumber 1.711 × 105 cm−1 and therefore corresponds to an energy
of 21.22 eV.Then, from eqn , 21.22 eV = 5.63 eV + Ii , so Ii = 15.59 eV. This
ionizationenergy is the energy needed to remove an electron from the
occupied molecular orbital with the highest energy of the N 2 molecule, the
2σg bonding orbital
Diketahui :
Ek = 5.63eV
l = 58.43 nm = 58.43 nm �10-7 cm / nm = 58.43 �10 -7 cm
1 1 ev
= 1,711�105cm -1 � E = 1,711�105cm -1 �
l 8065.5 cm -1
E photon = 21,22 eV
E photon = Ek + I i
21,22 eV = 5.63eV + I i
I i = 21,22 eV - 5.63eV = 15,59eV
Self-test 11.5 Under the same circumstances,
photoelectrons are also detected at 4.53 eV. To what
ionization energy does that correspond? Suggest an
[16.7 eV, 1πu]

What is the energy of an electron that has been ejected from
an orbital of ionization energy 11.0 eV by a photon of
radiation of wavelength 100 nm?
Heteronuclear diatomic molecules
The electron distribution in the covalent bond between the
atoms in a heteronuclear diatomic molecule is not shared
evenly because it is energetically favourable for the
electron pair to be found closer to one atom than the

(a) Polar bonds

two electrons in an orbital of the form

ψ = cAA + cBB
ψ = cAA + cBB

|cA|2 = |cB|2 cA = 0 and cB = 1

Fig. The atomic orbital energy levels of H and F atoms
and the molecular orbitals they form.
These points can be illustrated by considering HF, and
judging the energies of the atomic orbitals from the
ionization energies of the atoms. The general form of
the molecular orbitals is

ψ = cχH + cFχF