B.

Tech Chemistry
Course Code and Name :18CYB101J Chemistry
(AY 2020-2021)

Dr. P. Panneerselvam
Assistant Professor (Sr.G)
Department of Chemistry
SRMIST, Kattankulathur-603 203
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https://www.slideshare.net/tasmiakhan792
74/molecular-orbital-theory-lecture
 Homonuclear Diatomic Molecules Dr. P. Panneerselvam
• Hydrogen molecule (H2): Dihydrogen molecule belongs to the family of
diatomic molecules, which consists of two hydrogen atoms bonded to
each other by a covalent bond. According to the atomic number
of hydrogen, it has only one electron in its 1s orbital. The electronic
configuration of H2 molecule is given as:
H2: (σ1s)2
Bond order = = = 1
Due to the absence of unpaired electrons in the hydrogen molecule, it is
diamagnetic in nature.
 Dr. P. Panneerselvam

Molecular Orbital diagram of Hetero nuclear diatomic

molecule :
Molecular Orbital diagram of Carbon monoxide
molecule (CO):
Total electrons:6+8 =14
CO =σ1s2,σ*1s2,σ2s2,σ*2s2, σ2px2, π2py2= π2pz2.
Nb=10
Na=4
B.O =0.5 (Nb-Na)
B.O=0.5(10-4)
B.O= 3
• The conditions that are required for the linear combination of atomic orbitals are as
follows:
• Same Energy of Combining Orbitals
• The atomic orbitals combining to form molecular orbitals should have comparable
energy. This means that 2p orbital of an atom can combine with another 2p orbital of
another atom but 1s and 2p cannot combine together as they have appreciable energy
difference.
• Same Symmetry about Molecular Axis
• The combining atoms should have the same symmetry around the molecular axis for
proper combination, otherwise, the electron density will be sparse. For e.g. all the sub-
orbitals of 2p have the same energy but still, 2pz orbital of an atom can only combine
with a 2pz orbital of another atom but cannot combine with 2px and 2py orbital as they
have a different axis of symmetry. In general, the z-axis is considered as the molecular
axis of symmetry.
• Proper Overlap between Atomic Orbitals
• The two atomic orbitals will combine to form molecular orbital if the overlap is proper.
Greater the extent of overlap of orbitals, greater will be the nuclear density between
the nuclei of the two atoms.
• The condition can be understood by two simple requirements. For the formation of
proper molecular orbital, proper energy and orientation are required. For proper
energy, the two atomic orbitals should have the same energy and for the proper
orientation, the atomic orbitals should have proper overlap and the same molecular
axis of symmetry.
• If atom A and atom B have three p orbitals px, py and pz each, how can we decide which two orbitals will get
overlapped? In LCAO, it is a rule that two atomic orbitals must have similar energies. That means px will overlap
with px, similarly py with pyand pz with pz.

• Let’s see how px orbital gets overlapped with other px orbital. They can only meet head-on to overlap as they
are parallel to the inter-nuclear axis. The bond formed by their head-on overlapping is called sigma bond. But
there are two ways this can be done, either both overlapping lobes have similar sign or have opposite sings.
•
When both px orbitals have same signs they form sigma (σ) bonding molecular orbital. In this situation electron
density is increased between the two nuclei. And if both px orbitals have opposite signs they form sigma star
(σ*) antibonding molecular orbital. Here electron density is decreased between the nuclei and node is formed.
Node is a place where probability of finding electron is zero.
• In the last post we have discussed about the symmetry of MO, either they are gerade or ungerade. Let’s
examine σ and σ*and try to find out which one is gerade or ungerade.

The signs of the lobes of σ MO remain the same on rotating it along the line joining the two nuclei and
then about a line perpendicular to this line, which means it is gerade. But when we repeat similar
procedure with σ* MO, the signs of the lobes change, which means it is ungerade.

Dr. P. Panneerselvam
• Lets discuss the overlapping of py orbitals. They are perpendicular to the nuclear axis, that’s why they can
overlap only in sidewise manner and the bond is called pi (π) bond. Here also two possibilities arise, either
both lobes of overlapping orbitals have similar signs or one orbital get inverted at the time of overlapping
resulting in oppositely signed lobes.

Dr. P. Panneerselvam
• When both py orbitals have similar signs they form π bonding MO and in the other case they
form π* antibonding MO. You can clearly see that in π MO electron density is increased above and below
the inter-nuclear axis and node is formed at the inter-nuclear axis. While in π* MO electron density is
decreased everywhere and node is formed.
• Let’s examine their symmetry. When we rotate π MO along the line joining the two nuclei and then about
a line perpendicular to this line, the signs of the lobes change, which means it is ungerade. And when we
repeat similar procedure with π * MO, the signs of both lobes changes in an identical manner that’s why it
is gerade.
Next is pz orbital. Two pz orbital share the same axis so they can overlap
sidewise and form pi (π) bond. They also form πbonding MO and in other case
they form π* antibonding MO

MO due to to overlapping of s-p orbitals:

https://www.chemistrynotmystery.com/2014/09/linear-
combination-of-atomic-orbitals.html?q=s-
s+combination
 • To be able to explain how mixing atomic orbitals make molecule orbitals with
delocalized bonding
• The advantage of MO theory becomes more apparent when we think about π bonds,
especially in those situations where two or more π bonds are able to interact with one
another. Let’s first consider the π bond in ethene from an MO theory standpoint (in this
example we will be disregarding the various sigma bonds, and thinking only about the π
bond).
• According to MO theory, the two atomic 2pz orbitals combine to form two π molecular
orbitals, one a low-energy π bonding orbital and one a high-energy π-star (π*)
antibonding molecular orbital. These are sometimes denoted in molecular diagrams
with the Greek letter psi (Ψ) instead of π

Mixing of adjacent p atomic orbitals results in the bonding (π) and anti-bonding (π∗ ) molecular orbitals
 Dr. P. Panneerselvam
• In the bonding Ψ1 orbital, the two shaded lobes of the 2pz orbitals interact
constructively with each other, as do the two unshaded lobes (remember, the shading
choice represents mathematical (+) and (-) signs for the wave function). Therefore,
there is increased electron density between the nuclei in the molecular orbital – this is
why it is a bonding orbital. In the higher- energy antibonding Ψ2* orbital, the shaded
lobe of one 2pz orbital interacts destructively with the unshaded lobe of the second 2pz
orbital, leading to a node between the two nuclei and overall repulsion.

• Now, consider the 1,3-butadiene molecule. From valence orbital theory we might
expect that the C2-C3 bond in this molecule, because it is a σ bond that would rotate
freely.

The "single bond" in the 1,3-butadiene molecule is expected to rotate just like all sigma bonds.
 • However, it is experimentally found that there are significant barriers to rotation about
this bond (as well as about the C1-C2 and C3-C4 double bonds), and that the entire
molecule is planar. It is also observed that the C2-C3 bond, while longer than the C1-C2
and C3-C4 double bonds, is significantly shorter than a typical carbon-carbon single
bond.
• Molecular orbital theory accounts for these observations with the concept of
delocalized π bonds. In this picture, the four 2pz orbitals are all parallel to each other
(and perpendicular to the plane of the σ bonds), and thus there is π-overlap not just
between C1 and C2 and C3 and C4, but between C2 and C3 as well. The four atomic (2pz)
orbitals have combined to form four π molecular orbitals.

Molecular orbitals expected for mixing of the perpendicular p atomic orbitals of the
1,3-butadiene molecule.
 Dr. P. Panneerselvam

y2 is the Highest Occupied Molecular Orbital (HOMO)

y3 is the Lowest Unoccupied Molecular Orbital (LUMO)
The lowest energy molecular orbital, Ψ1, has zero nodes, and is a bonding MO. Slightly
higher in energy, but still lower than the isolated p orbitals, is the Ψ2 orbital. This orbital
has one node between C2 and C3, but is still a bonding orbital due to the two
constructive interactions between C1-C2 and C3-C4. The two higher-energy MO’s are
denoted Ψ3* and Ψ4*, and are antibonding. Notice that Ψ3* has two nodes and one
constructive interaction, while Ψ4* has three nodes and zero constructive interactions.
The energy of both of these antibonding molecular orbitals is higher than that of the 2pz
atomic orbitals of which they are composed.
 Dr. P. Panneerselvam
Benzene

Molecular orbital theory is especially helpful in explaining the unique properties of a class of
compounds called aromatics. Benzene, a common organic solvent, is the simplest example of an
aromatic compound. Although benzene is most often drawn with three double bonds and three
single bonds (Figure 11.6.4), it is known that all of the carbon-carbon bonds in benzene are
exactly the same length - 1.38 Å. This is shorter than a typical carbon-carbon single bond (about
1.54 Å), and slightly longer than a typical carbon-carbon double bond (about 1.34 Å).
• Benzene is also a cyclic molecule in which all of the ring atoms are sp2-hybridized that allows the π
electrons to be delocalized in molecular orbitals that extend all the way around the ring, above and
below the plane of the ring. For this to happen, of course, the ring must be planar – otherwise the 2pz
orbitals could not overlap properly. Benzene was experimentally confirmed to be flat molecule by Dame
Kathleen Londsale with X-ray crystallography.
• As shown in Figure 11.6.5, the cyclic array of six \2P_z\)-orbitals (one on each carbon) overlap to generate
six molecular orbitals, three bonding and three antibonding. The plus and minus signs shown in the
diagram do not represent electrostatic charge, but refer to phase signs in the equations that describe
these orbitals (in the diagram the phases are also color coded). When the phases correspond, the orbitals
overlap to generate a common region of like phase, with those orbitals having the greatest overlap (e.g.
π1) being lowest in energy. The remaining carbon valence electrons then occupy these molecular orbitals
in pairs, resulting in a fully occupied (6 electrons) set of bonding molecular orbitals.
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• https://www.youtube.com/watch?v=1841E4N
msHQ
• https://www.youtube.com/watch?v=eK8S51L
8juo
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https://www.slideshare.net/chems
ant/coordination-chemistry-cft
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Difference Between High Spin and Low Spin Complexes
• The key difference between high spin and low spin complexes is
that high spin complexes contain unpaired electrons, whereas
low spin complexes tend to contain paired electrons.
• What are High Spin Complexes?
• High spin complexes are coordination complexes containing
unpaired electrons at high energy levels. Since they contain
unpaired electrons, these high spin complexes are paramagnetic
complexes. This means these complexes can be attracted to an
external magnetic field.
• Low spin complexes are coordination complexes containing paired
electrons at low energy levels. Since there are no unpaired electrons
in the low spin complexes (all the electrons are paired), they
are diamagnetic. This means these compounds cannot be attracted
to an external magnetic field. The low energy splitting of a compound
occurs when the energy required to pair two electrons is lower than
the energy required to place an electron in a low energy state.
•
Dr. P. Panneerselvam
• Crystal Field Stabilization Energy
• In a chemical environment, the energy levels generally split as
directed by the symmetry of the local field surrounding the
metal ion. The energy difference between the eg and t2g
• levels is given as or 10Dq. It states that each electron that goes
into the lower t2g level stabilizes the system by an amount of -
4Dq and the electron that goes into eg level destabilizes the
system by +6Dq. That is the t2g is lowered by 4Dq and the eg
level is raised by +6Dq.
• For example, the net change in energy for d5 and d10 systems
will be zero as shown below.
• d5 :- 3(-4Dq) + 2(+6Dq) = -12Dq + 12Dq = 0
• d10 :- 6(-4Dq) + 4(+6Dq) = -24Dq + 24Dq = 0
• The decrease in energy caused by the splitting of the energy
levels is called the “Ligand Field Stabilization Energy (LFSE)”.
 Dr. P. Panneerselvam
spectrochemical series
• Thus, the crystal eld splitting depends on the eld produced
by the ligand and the charge on the metal ion. An
experimentally determined series based on the absorption
of light by coordination compound known as
spectrochemical series has been proposed.
Spectrochemical series arranges ligands in order of their
eld strength as:
• I < Br < Cl < F < OH < C O < NCS < EDTA < NH < en < CN <
CO
 Dr. P. Panneerselvam
• SPECTROCHEMICAL SERIES:
• We know that the Ligands which cause large degree of crystal filed
splitting are termed as strong field ligands. and Ligands that cause only a
small degree of crystal filed splitting are termed as weak field ligands. The
common ligands can be arranged in ascending order of crystal field
splitting energy. The order remains practically constant for different
metals and this series is called the spectrochemical series.
• Tetahedral complex (sp3):

In a tetrahedral field : Consider a cube such that a metal atom

or ion is situated at its centre of symmetry through which the
axis of geometry are passing and joining the face centres of
this cube. Therefore, lobes of eg orbitals will be directed
towards the face centres but those of t2g orbitals will be
pointing towards edge centres. Now consider 4
monodentate ligands approaching the metal, the 4
alternate corners of this cube so as to make a tetrahedron.

• Thus it is clear that t2g orbitals are nearer to the ligands than
the eg orbitals. Hence t2g orbitals will experience more
repulsion than eg orbitals. Therefore, crystal field splitting will
be reversed of octahedral field which can be shown as below.
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