Principles of Chemistry 1 (KEMPRN1)

4fz3
LECTURE 15
4fxz2 4fyz2 4fz(x2–2y2) 4fxyz 4fy(3x2–y2) 4fx(x2–3y2
Molecular Orbital Theory

Dr. Joel Garcia

Department of Chemistry
Relationship between Hybridization and
the VSEPR Model.

sp

sp2

sp3

sp3dz2

sp3dz2dx2-y2
Method of orbital overlap by VBT does not explain
why carbon in CH4 forms four bonds.

2p

2s
C
2s22p2
Electron promotion followed by hybridization
can explain the bonding scheme in CH4.

promotion of
2p electron 2p hybridize

sp3 sp3 sp3 sp3

2s 2s
C
2s22p2
VBT can also be applied to rationalize the bond
equivalence of four C-H bonds.

promotion of
2p electron 2p hybridize

sp3 sp3 sp3 sp3

2s 2s
C
2s22p2

𝜎Csp -Hs
3

(all C-H bonds)

What about VBT treatment for multiple bonds?

2p

2s
C
2s22p2
What about VBT treatment for multiple bonds?

promotion of
2p electron 2p hybridize p
sp2 sp2 sp2
2s 2s
C
2s22p2
What about VBT treatment for multiple bonds?

promotion of
2p electron 2p hybridize p
sp2 sp2 sp2
2s 2s
C
2s22p2
 Bonding in Ethylene, 𝑪𝟐 𝑯𝟒

Sigma bond σ – electron density between the 2 atoms

Pi bond π – electron density above and below plane of nuclei

of the bonding atoms 9
 Bonding in Ethylene, 𝑪𝟐 𝑯𝟒

Sigma bond σ – electron density between the 2 atoms

Pi bond π – electron density above and below plane of nuclei

of the bonding atoms 10
 Bonding in Ethylene, 𝑪𝟐 𝑯𝟒

Sigma bond σ – electron density between the 2 atoms

Pi bond π – electron density above and below plane of nuclei

of the bonding atoms 11
 Sigma 𝛔 and Pi Bonds 𝝅

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

12
What about VBT treatment for multiple bonds?

promotion of
2p electron 2p hybridize p p
sp sp
2s 2s
C
2s22p2
Bonding in Acetylene, 𝐂𝟐 𝐇𝟐

14
Bonding in Acetylene, 𝐂𝟐 𝐇𝟐

15
Bonding in Acetylene, 𝐂𝟐 𝐇𝟐

16
The s and p bonds in acetylene (C2H2)

Each C is sp hybridized and has

two unhybridized p orbitals.
The s and p bonds in acetylene (C2H2)

Each C is sp hybridized and has

two unhybridized p orbitals.
The s and p bonds in acetylene (C2H2)

Each C is sp hybridized and has

two unhybridized p orbitals.
The s and p bonds in acetylene (C2H2)

Each C is sp hybridized and has

two unhybridized p orbitals.
Exercise
1. Explain why an sp3 hybridization can be applied to H2O, but
not to XeF2.
2. Give a suitable hybridization scheme for the central atom in
each of the following:
(a) NH4+
(b) H2S
(c) BBr3
(d) NF3
(e) H3O+
3. Label all the bonds present in the compound below to
describe the hybridization scheme used by the central atoms
and the nature of AOs overlap in each of the bonds in the
molecule.
 Valence Bond Theory: Limitation
and Difference with MOT
1. VBT cannot explain why O2 is paramagnetic. According to
VBT, all the electrons in O2 are paired and oxygen should
therefore be diamagnetic.
2. Unlike VBT, which uses orbitals that are assigned to one
specific atom, MO Theory uses the combination of AO’s to
yield MO’s that are delocalized over the entire molecule
rather than being localized on their constituent atoms.

22
 Valence Bond Theory: Limitation
and Difference with MOT
1. VBT cannot explain why O2 is paramagnetic. According to
VBT, all the electrons in O2 are paired and oxygen should
therefore be diamagnetic.
2. Unlike VBT, which uses orbitals that are assigned to one
specific atom, MO Theory uses the combination of AO’s to
yield MO’s that are delocalized over the entire molecule
rather than being localized on their constituent atoms.

23
 Energy Levels of Bonding and Antibonding
Molecular Orbitals in Hydrogen 𝐇𝟐

A bonding molecular orbital has lower energy and greater

stability than the atomic orbitals from which it was formed.

An antibonding molecular orbital has higher energy and

lower stability than the atomic orbitals from which it was
formed. 24
Constructive and Destructive Interference

25
 Energy Levels of Bonding and Antibonding
Molecular Orbitals in Hydrogen 𝐇𝟐

AAbonding
bondingmolecular
molecularorbital
orbitalhas
haslower
lowerenergy
energyandandgreater
greater
stability
stabilitythan
thanthe
theatomic
atomicorbitals
orbitalsfrom
fromwhich
whichititwas
wasformed.
formed.

26
 Energy Levels of Bonding and Antibonding
Molecular Orbitals in Hydrogen 𝐇𝟐

A bonding molecular orbital has lower energy and greater

stability than the atomic orbitals from which it was formed.

27
Constructive and Destructive Interference

28
 Energy Levels of Bonding and Antibonding
Molecular Orbitals in Hydrogen 𝐇𝟐

A bonding molecular orbital has lower energy and greater

stability than the atomic orbitals from which it was formed.

An antibonding molecular orbital has higher energy and

lower stability than the atomic orbitals from which it was
formed. 29
Two Possible Interactions Between Two Equivalent p Orbitals

30
Two Possible Interactions Between Two Equivalent p Orbitals

31
 Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

32
 Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

33
 Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

34
 Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

35
 Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

36
 Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

37
MO diagram for He2+ and He2
MO diagram for He2+ and He2
MO diagram for He2+ and He2

He2+ bond order = ½

* 1
(σ1s)2(σ 1s)
MO diagram for He2+ and He2

He2+ bond order = ½

* 1
(σ1s)2(σ 1s)
MO diagram for He2+ and He2

He2+ bond order = ½ He2 bond order = 0

* 1 * 2
(σ1s)2(σ 1s) (σ1s)2(σ 1s)
 Molecular Orbital (MO) Configurations
General molecular orbital energy level diagram for the
second-period homonuclear diatomic molecules Li/, Be/, B/,
C/, and N/.

43
Relative MO Energy Levels for Period 2
Homonuclear Diatomic Molecules.
with 2s-2p
mixing

MO energy levels
for B2, C2, and N2
 Relative MO Energy Levels for Period 2
Homonuclear Diatomic Molecules.
without 2s-2p with 2s-2p
mixing mixing

MO energy levels MO energy levels

for O2, F2, and Ne2 for B2, C2, and N2
MO occupancy and
molecular properties
for B2 through Ne2.
MO occupancy and
molecular properties
for B2 through Ne2.
MO occupancy and
molecular properties
for B2 through Ne2.
MO occupancy and
molecular properties
for B2 through Ne2.
MO occupancy and
molecular properties
for B2 through Ne2.
MO occupancy and
molecular properties
for B2 through Ne2.
MO occupancy and
molecular properties
for B2 through Ne2.
Example 10.6
The N/4 ion can be prepared by bombarding the N/ molecule
with fast-moving electrons.

Predict the following properties of N/4:

(a) electron configuration

(b) bond order

(c) magnetic properties

(d) bond length relative to the bond length of N/ (is it longer or

shorter?)
Example 10.6 (2)
Solution From Table 10.5 we can deduce the properties of
ions generated from the homonuclear diatomic molecules.

(a) Because N/4 has one fewer electron than N/, its electron
configuration is

/ / / 5
/ ∗ / ∗ /
𝜎56 𝜎56 𝜎/6 𝜎/6 𝜋/9: 𝜋/9; 𝜎/9<

(b) The bond order of N/4 is found by using Equation (10.2):

bond order = 5⁄/ 9 − 4 = 2.5

(c) N/4 has one unpaired electron, so it is paramagnetic

Example 10.6 (3)
(d) Because the electrons in the bonding molecular orbitals are
responsible for holding the atoms together, N/4 should have
a weaker and, therefore, longer bond than N/. (In fact, the
bond length of N/4 is 112 pm, compared with 110 pm
for N/.)

Check Because an electron is removed from a bonding

molecular orbital, we expect the bond order to decrease. The
N/4 ion has an odd number of electrons (13), so it should be
paramagnetic.