Module1 (9 of 12)-MKM
Pi (π) molecular orbitals of butadiene and benzene and aromaticity
1,3-Butadiene
The structure of 1,3-Butdiene consists of two conjugated double bonds. The structure has four
sp2 hybridized C atoms. Each atoms contributes a p atomic orbital consisting of one electron.
The combination of π molecular orbitals of two ethene molecules produces π
molecular orbitals for which we need to make an in-phase combination and out- of
–phase combination of π and π* of ethene ,respectively.
Figure 1: Molecular Orbital of 1,3-butadiene
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Figure 1 represents the relative energies of π molecular orbitals of 1,3-butadiene,
which is a derived compound of ethene. The energy of the p orbital of a C atom is
denoted by the horizontal centre [Link] orbitals lying below the horizontal line
are bonding , whereas the orbitals above it are antibonding.
Each p orbital contributes one electron, resulting in the arrangement of four
electrons from four p orbitals which combine in four different ways to form four
molecular orbitals designated as ψ1, ψ2, ψ3 and ψ4.
• Ψ1 has bonding interaction between C1-C2 , C2-C3, and C3-C4 . Therefore ,
there exists 3 bonding interactions.
• Ψ2 has bonding interaction between C1-C2 and C3-C4 and antibonding
interaction between C2-C3. Therefore , they have single bonding interaction.
It is the highest occupied molecular orbital (HOMO).
• Ψ3 has bonding interaction between C2-C3 but antibonding interaction
between C1-C2 and C3-C4. Therefore, they have a single antibonding
interaction. It is the lowest unoccupied molecular orbital (LUMO).
• Ψ4 has antibonding interaction between C1-C2, C2-C3 and C3-C4.
Therefore, they have 3 antibonding interaction.
Thus, out of four orbitals available, ψ1 and ψ2 are bonding molecular orbitals,
whereas ψ3 and ψ4 are antobonding molecular orbitals. The p orbitals from
which these orbitlas are formed are at higher energy than the two bonding MOs,
whereas the two antibonding MOs are higher in energy than the p orbitals. The
energy in a molecular orbital increases with the rise in the number of nodes.
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Benzene:
Molecular orbital theory of Benzene
The molecular orbital theory provides the fullest description of the benzene ring. It
is based on spectroscopic and X- ray diffraction methods according to which
benzene molecule is hexagonal planner structure. Each molecular orbital of
benzene consists of a combination of the six p orbitals. Bonding interaction occurs
when the orbitals line up in such a way that each lobe overlapping another p orbital
has same sings. An orbital lining up with an opposite sign creates an antibonding
interaction and a node between orbitals. Figure1 shows the overlapping of p
orbitals.
Figure1: Overlapping of p orbitals
The three π bonds of benzene are formed by the overlapping of six p orbitals on
six adjacent carbon [Link] six p orbitals form six molecular orbitals by
combining in six different ways. The six MOs are designated as ψ1, ψ2, ψ3, ψ4,
ψ5 and ψ6, of these six MOs, ψ1, ψ2 and ψ3 are bonding molecular orbitals,
whereas ψ4, ψ5 and ψ6 are antibonding orbitals.
Figure2 : Molecular Orbital of Benzene
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Each molecule orbital can accommodate two electrons having opposite
[Link] addition of six electrons to the molecular orbitals begning from
the lowest energy molecule orbital result in the filling of all three bonding
molecular orbitals. The three higher energy antibonding orbitals remain empty.
Due to the presence of three filled bonding molecular orbitals in benzene, it
possesses a closed bonding shell which makes it stable.
Q. Why is benzene extra-ordinary stable though it contains three double bonds?
Answer: Benzene is extra ordinary stable though it contains three double bonds
because π electrons in benzene are delocalised. The absence of pure double bond
in benzene accounts for the extraordinary stability. This also accounts for the
reluctance of benzene to show addition reaction under normal conditions.
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Aromaticity
The necessary conditions for a molecule to be aromatic are;-
(i) It should be planar (Planarity)
(ii) The π electrons in the ring are completely delocalised (Delocalisation)
(iii) It should contain (4n+2) π electrons in the ring where n are an integer
(n = 0, 1,2…..) [(4n+2) π electrons/Huckel rule]
According to Huckel rule only those planner cyclic systems having conjugated
double bonds display aromatic character which have (4n+2) π electrons where n is
integer and may be 0,1,2,3…….. because such system possess substantial
resonance energy. [n=0 π =2 ; n=1 π =6 ; n=2 π =10……… ]
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