Mo 2

Doubts from Moodle
• i understand that we ignore the sigma bond because they are not in the plane of pi. but if we
consider the particle nature of electrons, wont the sigma electrons affect the pi electrons in
some way?
• Mam you said there is one nodal plane in pi ABMO but when you drew it looks like there are 2
nodal planes along conventional x and y axes. Also it looks like there is one nodal plane in pi
bmo along conventional x axis but you said 0. Why?
• Nodes in MO – Nodes formed as a result of mixing of AO (atomic orbitals)
• AO nodes ignored
1
Doubts from Moodle
• Mam, when to different atoms combine then why is it that the more electronegative element
contributes more to the BMO and the less electronegative element contributes more to the
AMO?
• If there's a destructive interference of two out of phase orbitals of the same subshell , lets say
1s(+ve) and 1s(-ve) so their Wave equations should be of the same magnitude but different
sign bcz they are just exactly same orbitals ? It means they should just add up to zero. But the
graph of the same, something like that. Can you please explain mam ?
2
Doubts from Moodle
• Ma'am, today we dealt with one pi bond between two atoms. What will be the case when
there were two pi bonds or delta bond involved
Stay tuned ☺
• You told us the Molecular Orbital theory but it is more about mathematical representation. I
wanted to ask, how thus this actually look like in a molecule like we have shell and subshells,
so how this BO and ABO are arranged?
We are focusing on pi MOs. The BOs and ABOs are arranged in increasing order of number of
nodes. Electrons in the molecule fill these MOs starting from lowest energy MO. Stay tuned ☺
Remember the AOs – defines the space for probability of finding electron in atom
Mos – defines the space for probability of finding electron in a molecule
3
Doubts from Moodle
• So, basically there was a pie bond and a sigma bond between the two carbons? But in the representation
showing the electrons there were only two electrons. how is that even possible ? As there should have been 4
electrons? I think that I got mixed up with what was taught in class 12th and here....In fact, it was taught that
both of them are pie bonds only due to sp mixing
4 electrons for pi bond + sigma bond
2 electrons for pi bond (Huckel theory, we ignored the sigma), will repeat in this class
• Maam, today morning we only considered the wave function of the considered orbitals when combining for
LCAO, but what about the associated angular momentum of the electrons in those orbitals combining to form
the molecular orbitals?
Stay tuned for CH107 ☺
• mam please clarify that is nodes or nodal planes only the region where probability of finding electrons is zero
and it do not contribute to stability of atoms or molecules in any way?
it is clarified that in case of MO nodes are formed due to destructive interference, but how does nodes form in
case of atomic orbitals?
https://winter.group.shef.ac.uk/orbitron/
4
Ethylene – Simplified MO picture
The σ – framework neglected as it is in the nodal plane of the p atomic orbitals
Phase inversion
(node)
Qualitative Picture – Hückel’s MO

Calculating Energies of MOs
Energy of each ith MO given by
EiMO = α + mjβ mj = 2 [Cos (jπ/n+1)]
Coulomb Resonance n = no: of carbon atoms

Integral Integral j = 1 to n
Coulomb integral – refers to energy of an electron in the field of its own nucleus , [can be
taken as valence state ionization potential]
Resonance integral - refers to energy of an electron in the field of the neighboring nucleus ,
[can be taken as the interaction between neighboring atomic orbitals]
Note: α and β are negative by definition

The α and β are not calculated as numerical values.
The energies are expressed in terms of these quantities
Ethylene – Energies of MOs
E2 = α - β
E1 = α + β
Total Energy = Σ (ne-i  Ei); ne- = no. of electrons

For Ethylene = 2(α + β) = 2α + 2β
Applying to Larger Conjugated Systems
Molecular Orbital Picture
Let us look at the π-bonding interactions closely
The σ – framework neglected as it is in the nodal plane
interact π/ MOs
n n
Qualitative Picture – Hückel’s MO

MO Construction Acyclic Conjugated Polyenes
antibonding MOs
Energy
n AO Non bonding
bonding MOs
Lowest energy MO 0 nodes,

next MO 1 node
nth MO (n-1) nodes
The nodes are placed symmetrically
When n is even – n/2 bonding and n/2 antibonding MOs exist
When n is odd – (n-1)/2 bonding, 1 non-bonding and (n-1)/2 antibonding MOs exist
Activity: Draw the MOs of Butadiene
10
Butadiene MOs
Ψ4 = c1φ1 - c2φ2 + c3φ3 - c4φ4
E4 = a - 1.62b
Write the
wave equation Ψ3 = c1φ1 - c2φ2 - c3φ3 + c4φ4
for each MO LUMO E3 = a - 0.62b
Energy
Write the Ψ2 = c1φ1 + c2φ2 - c3φ3 - c4φ4

energy for E2 = a + 0.62b
HOMO
each MO
Ψ1 = c1φ1 + c2φ2 + c3φ3 + c4φ4
E1 = a + 1.62b
MOs of Larger Conjugated Polyenes
• 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. ψ1 - 0 nodes
ψ2 - 1 node
ψn - n-1 nodes
Again: Remember to ignore the nodes of the AO
• When you draw MOs place the nodes symmetrically

Activity: Draw the MOs of Hexatriene
13
A Small Activity
• Go to www.menti.com –
• Use code 54621591
or directly go to
https://www.menti.com/n21kgz5uod
Happy answering ☺
MOs of Hexatriene
ψ6
ψ5
ψ4
Energy
ψ3
ψ2
ψ1

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Doubts from Moodle

• Nodes in MO – Nodes formed as a result of mixing of AO (atomic orbitals)

Qualitative Picture – Hückel’s MO

Coulomb Resonance n = no: of carbon atoms

Note: α and β are negative by definition

Total Energy = Σ (ne-i  Ei); ne- = no. of electrons

interact π/ MOs

Qualitative Picture – Hückel’s MO

Lowest energy MO 0 nodes,

Write the Ψ2 = c1φ1 + c2φ2 - c3φ3 - c4φ4

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

• When you draw MOs place the nodes symmetrically

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