SS 3.

3: Molecular orbital theory

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Molecular orbitals of H2:
+ = CA1s(A) + CB1s(B)
- = CA1s(A) - CB1s(B)

The relative sign of the coefficients determine

whether the atomic orbital’s influence is constructive or destructive.
 Increase or decrease of electron density between nuclei
SS 3.3: Molecular orbital theory

Heteronuclear diatomic molecules:

 = CA (A) + CB (B) + . . . . . .

 are atomic orbitals on atom A and atom B

CA and CB are coefficients that indicate the size of contribution from atomic
orbitals to molecular orbitals (CA  CB)
SS 3.3: Molecular orbital theory

Heteronuclear diatomic molecules:

The contribution of atomic orbitals to molecular orbitals can be
determined by C2.

The larger C2 is, the larger the contribution of the atomic orbital to the
molecular orbital. (C’B2 > C’A2)

Example:
CA2 > CB2
The molecular orbital is mainly composed of
A’s atomic orbital.

An electron that occupies the molecular orbital

is more likely to be found near atom A than
atom B.
(CA2 > CB2)
SS 3.3: Molecular orbital theory

Heteronuclear diatomic molecules:

The greater contribution to a die bonding molecular orbital normally
comes from the more electronegative atom .
• The bonding e- are likely to be found near that atom
(Energetically favourable location)

The greater contribution to the antibonding orbital is from the less

electronegative atom.

Heteronuclear diatomic molecule is polar.

Extreme case of polar covalent bonds are ionic bonds.

(covalent bonds formed by an e- pair that is shared unequally)
SS 3.3: Molecular orbital theory

Heteronuclear diatomic molecules:

There is an energy mismatch between the two sets of atomic orbitals.
The relative positions of the two atomic orbitals reflect on the
ionisation energy of the atoms.
SS 3.3: Molecular orbital theory

Heteronuclear diatomic molecules:

The more their energies differ, the smaller the effect two
wavefunctions will have on each other.

-

B
-
Energy

A A

+

+
Due to interference
of wavefunctions
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):

Valence orbitals available for molecular orbital formation:

1s of H 1s1
2s and 2p of F [He]2s22p5

1 + 7 = 8 valence electrons to accommodate the MO

H(1s) + F(2s + (3 x 2p)) = 5 AO => 5 MO

SS 3.3: Molecular orbital theory

Heteronuclear diatomic molecules:

The 1s AO of hydrogen has a relatively high energy when compared to
the 2p AO of fluorine. (Also note the relative difference between the 2p
and 2s AO of fluorine)
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):

H 1s

F 2p
Energy

F 2s
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):
1s/pz*

2p*

H 1s

F 2p
2p
Energy

1s/pz

2s*

F 2s

1s
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):

 orbitals of HF:
Constructed by allowing 1s orbital of H to overlap the 2s and 2pz orbitals of
F.

Three atomic orbitals combine to form three  molecular orbitals:

 = C11s(H) + C22s(F) + C32pz(F)

SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):
1s/pz*

2p*

H 1s

F 2p
2p
Energy

1s/pz

2s*

F 2s

1s
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):
3
2p*

H 1s

F 2p
2p
Energy

2

F 2s

1
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):

 orbitals of HF:
2px and 2py of F are unaffected as they have  symmetry and there is no
valence orbital of H of that symmetry.
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):
3

H 1s
1
F 2p
Energy

2

F 2s

1
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):

 orbitals of HF:
2px and 2py are unaffected as they have  symmetry and there is no
valence orbital of H of that symmetry.

The  orbitals re therefore nonbonding orbitals.

• Nonbonding orbitals are orbitals that have a nonbonding or antibonding

character .
• And can be confined to one atom in a diatomic molecule.
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):
122214
3

H 1s
1
F 2p
Energy

2

F 2s

1
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):
122214
3 Mainly H

H 1s
1
F 2p
Energy

Mainly F

2

F 2s

Mainly F 1
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):
122214
3 LUMO

H 1s
1
HOMO F 2p
Energy

Nonbonding orbital
2
Bonding orbital

F 2s

1
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (HF):

HF: 122214

NB
All electrons fill orbitals that are mainly on the F atom.

HF polar
Partial negative charge on the F atom (Dipole)

Note that g (gerade) and u (ungerade) notations are no longer used,

since there is no symmetry.
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):

Both C and O have 2s and 2p orbitals that can participate in the formation
of  and  molecular orbitals.
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):

Valence orbitals available for the formation of molecular orbitals:

2s and 2p of C [He]2s22p2
2s and 2p of O [He]2s22p4

4 + 6 = 10 valence electrons to occupy MO

C(2s + (3 x 2p)) + O(2s + (3 x 2p)) = 8 AO => 8 MO

SS 3.3: Molecular orbital theory

Heteronuclear diatomic molecules (CO):

Carbon’s 2p and 2s are higher in energy than oxygen’s 2p and 2s AO
respectively. Note the energy difference between oxygen’s 2s and 2p in
comparison with that of carbon.
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):

Valence orbitals available for the formation of molecular orbitals:

2s and 2p of C [He]2s22p2
2s and 2p of O [He]2s22p4

4 + 6 = 10 valence electrons to occupy MO

C(2s + (3 x 2p)) + O(2s + (3 x 2p)) = 8 AO => 8 MO

SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):

C 2p

O 2p
Energy

C 2s

O 2s
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules:

s/pzr

p
Energy

s/pzl

Mixing of s and pz AO to form two new  MO.

SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):
4
12221432
2
LUMO
C 2p

O 2p
3
Energy

HOMO
C 2s
1

2
O 2s

1
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):
• 1 - localized mostly on the O atom
- NBMO
• 2 - BMO
• 1 - mainly C2p character
- -BMO
• 3 - mainly C2pz character
- located on the C atom
- largely NBMO (HOMO)
• 2 - mainly C2p character
- -ABMO

Frontier orbitals of CO – characteristic feature of transition metal carbonyls

SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):
4
CO: 12221432
LUMO 2

-11 C 2p

3
-13 HOMO O 2p

-19 C 2s 1
Energy (eV)

2
𝛿− 𝛿+
-34 O 2s
:C O: 1
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):
Both C and O have 2s and 2p orbitals that can participate in the formation
of  and  molecular orbitals.

Although the difference in electronegativity between C and O is large,

the dipole moment of the CO molecule is small.

Despite C being the less electronegative atom, the negative end of the
dipole is on the C atom.

Lone pairs and bonding pairs have a complex distribution.

It is wrong to conclude that the polarity is only dependent on

electronegativity when the antibonding orbitals are filled.
SS 3.3: Molecular orbital theory
Heteronuclear diatomic molecules (CO):

Molecular orbitals of CO:

The size of the atomic orbitals

indicate the degree of
contribution to the molecular
orbital.