Doubts from Moodle

• Ma'am,in the molecular orbitals of benzene the psi4 orbital and the psi5 orbital both have two
nodes but in the psi 5 orbital we can see that there are two constructive interaction and in psi
4 there are no constructive interaction.So why is it that both psi 4 and psi 5 orbitals are kept at
the same energy level should'nt the psi 5 orbital be at a lower energy level?

1
MOs of Conjugated Cyclic Systems

2
 MOs of Larger Conjugated Cyclic Systems
• The lowest energy orbital is always symmetric with respect to the
principal mirror plane

• The energy of the MO increases as the no: of nodes increases

Eg. Level 1 - 0 nodes
Level 2 - 1 node
Level n - n-1 nodes

Remember:
Ignore the nodes of the AO
There can be multiple MOs with same no. of nodes
The nodal planes cut the entire molecule!
MOs – Conjugated Cyclic Systems
MOs of Benzene

Ψ6

Ψ4 Ψ5

Ψ2 Ψ3

Ψ1

In this case there are degenerate MOs!

 Calculating Energies of the MOs
Energy of each ith MO given by
EMO = α + mJβ mj = 2 [Cos 2jπ/n]

n = no: of carbon atoms

Coulomb Resonance
j = 0 to 1…. to n/2, when n even
Integral Integral J = 0 to  (n-1)/2, when n odd
Energies of Benzene MOs
Total energy?
(j = 3)

(j = 2)

(j = 1)

(j = 0) Additional Stabilization in Benzene = 2b

 What does 2β Mean?
Can this stabilization be quantified? (assuming isolated double
bond)

-151 KJ/mol
(observed)
Energy

(observed)

-240 KJ/mol

-232 KJ/mol

-209 KJ/mol
-120 KJ/mol

Stabilization = 151 KJ/mol or 36 Kcal/mol = 2β

Resonance/Delocalization Energy
 Easier Way to Draw MOs – Cyclic Systems
Frost’s Circle Method

• Draw a circle of diameter 4β

• Draw the polygon such that one of its vertices is at the
bottom

Antibonding

Nonbonding

Bonding
 Short Exercise
Draw the MOs (using the Frost Circle Method ) for Cyclobutadiene.

Would you call this aromatic based on stability?

Homework : Draw the MOs using Frost’s circle method for cyclooctatetraene dication. Is
it aromatic? No need to calculate energies
 Huckel’s Rules
Brings together the Resonance as well as MO considerations

• Molecule should be cyclic, planar with uninterrupted cloud of electrons

above and below the ring plane
and should have 4n + 2 π electrons - Aromatic

• Analogous systems with 4n p electrons are described as Antiaromatic

 Classification

Aromatic Planar and cyclic

Complete conjugation
(4n + 2) π electrons

Antiaromatic Planar and cyclic

Complete conjugation
4n π electrons

Nonaromatic Not planar or interrupted conjugation

(4n + 2) or 4 nπ electrons
 Examples
Annulenes – Monocyclic structures with complete conjugation i.e. Alternate
single and double bonds

Represented as [n] - Annulene

No: of C atoms in the ring

Nonaromatic Aromatic Antiaromatic

 A Small Activity

• Go to www.menti.com –
• Use code 35044432
Or go to
https://www.menti.com/8fc302
Start playing the game
 Let us Classify the Following

Nonaromatic
Antiaromatic

Aromatic

Aromatic

Nonaromatic

Aromatic Aromatic Aromatic

 Heterocyclic Ring Systems
Aromatic Heterocyclic Systems

Lp does not contribute to π- system

Lp contributes to π- system

No contribution

contributes
One lp contributes
 Fused Aromatic Systems
Although Huckel’s Rules are for monocyclic systems - concept of aromaticity can be
extended to fused systems

Aromatic Systems 10 and 14 π electron systems

Heterocyclic Aromatic Analogs

Interesting Fused Systems

Stabilizing dipolar resonance structures