Doubts from Moodle

• Maam, in slide no 8 you told that When n is odd (n-1)/2 bonding, 1 non-bonding and (n-1)/2
antibonding MOs exist but what is a non bonding MO here?like when we fill electrons we fill
them only in bonding and anti bonding orbitals right? please clear my confusion,thanks.
Non-bonding implies same energy as AO. Electrons fill orbitals in the order of increasing E.
So non-bonding can also be filled. More on non-bonding soon. Stay tuned ☺

• Ma'am you said that we ignore sigma bonds in ethene as they lie in nodal plane of pi bonds.
But isn't the sigma bond involving 2s orbital of carbon atom in all planes as 2s orbital is
spherical? So won't that sigma bond be in plane with pi bonds?
We are looking at a simplified picture zooming into only the pi MOs. As per electron
distribution probability, even with s orbitals probability is max closer to nucleus.

A look at all MOs - http://csi.chemie.tu-

darmstadt.de/ak/immel/tutorials/orbitals/molecular/ethene.html (extra reading not in
the scope of syllabus) 1
 Doubts from Moodle
• Regarding sigma bond, what is the meaning of :No nodes along internuclear axis?

• what does mean electron as a wave ? does it mean, the electron moves in wave path or the
electron itself a wave or the electron is associated with wave mam, in orbital is the electron
moving in a wave path or the electron itself orbiting the nucleus in wave form

Electron itself as a wave. The orbital is the square of electron wavefunction and only gives
the region of probability of finding an electron. The fact that electrons have a wave nature was
discovered by physicists and chemists seeing inspiration from the understanding of light and
optics.

Additional reading material (not in syllabus) –Nobel lecture by De Broglie

https://www.nobelprize.org/prizes/physics/1929/broglie/lecture/ 2
 Doubts from Moodle
• Maam uptil now we combined 2 atomic orbitals to form 2 molecular orbitals but when you
showed us the butadiene example there were 4 molecular orbitals formed and each orbital
was using 4 atomic orbital.
n AOs form n MOs . In butadiene 4 p orbitals (think of two double bonds) mix in different
combinations of wavefunction of the AOs to give 4 Mos

• In lecture 2 someone asked that if the beta factor of energy is only due to neighbouring nuclei
or due to combination of both nuclei, you said that it was due to combination of both nuclei,
so are we considering the energy due to its own nuclei twice, once in alpha factor as well as in
beta factor?
Resonance integral or beta - refers to energy of an electron in the field of the neighboring
nucleus , [can be taken as the interaction between neighboring atomic orbitals]

• Can we apply the expression for E imo to other molecules such as he 2 for example. ( For he2 ,
the total energy comes out as 4 alpha , and alpha being negative would mean he2 is stable ? )
Only applicable to acyclic pi conjugated systems 3
 Doubts from Moodle
• In Calculating Energies of MOs, In the expression to find mj, you told that "n is the no of
carbon atoms, only those which we are considering for the pi bond, so for ethylene, n will be
2" but if we are considering only those C atoms which are participating in pi bond formation
then for any molecule, n will be equal to 2. If yes, then why are we still taking a variable there
instead of just a "2" and if no, please explain where I am wrong.

For butadiene, n=4, hexatriene n=6 etc. Total number of carbons participating in conjugation

4
 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. ψ 1 - 0 nodes
ψ 2 - 1 node
ψ n - n-1 nodes
Again: Remember to ignore the nodes of the AO

• When you draw MOs place the nodes symmetrically

 Butadiene MOs
Ψ 4 = c1φ 1 - c2φ 2 + c3φ 3 - c4φ 4
E4 = a - 1.62b

Ψ 3 = c1φ 1 - c2φ 2 - c3φ 3 + c4φ 4

Total Energy of Butadiene = LUMO E3 = a - 0.62b

Energy
2 (a + 1.62b) + 2(a + 1.62b)
= 4 a + 4.48b
Ψ 2 = c1φ 1 + c2φ 2 - c3φ 3 - c4φ 4
Extra stabilization of 0.48b
E2 = a + 0.62b
Compared to two isolated HOMO
ethene
Ψ 1 = c1φ 1 + c2φ 2 + c3φ 3 + c4φ 4
E1 = a + 1.62b
 MOs of Hexatriene
ψ6

ψ5

ψ4
Energy

ψ3

ψ2

ψ1
 MOs – See any patterns?
ψ6
ψ4

ψ2 ψ5

LUMO ψ3
ψ4
LUMO LUMO
Energy

ψ3

ψ2 HOMO
ψ1 ψ2
HOMO
HOMO ψ1
ψ1

2p 4p 6p
Draw the MOs of Allyl Cation

9
 MOs of Allyl System
ψ3

Antibonding
Energy

ψ2

Non-bonding

ψ1

2e⁻ 3e⁻ 4e⁻

Bonding
Cation Radical Anion
Summary: Acyclic Conjugated Systems
What is the trend in HOMO-LUMO gap?
 Polyenes as Semiconductors
Approximate Analogy Between Molecular and Solid-State Terminologies
HOMO Valence Band
LUMO Conduction Band
HOMO-LUMO gap Band gap

Conducting polymer

Conductivity increases
Answer – The HOMO-LUMO gap decreases ☺
MOs of Conjugated Cyclic Systems

13
 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!