Introduction to Molecular

Orbital Theory



6
7
8
hybridization
Mixing 2s and 2p: requires degeneracy to maintain eigenfunctions of AOs.
Otherwise, the hybrid orbital is an average value for the atom, not an exact solution.
This makes sense when ligands impose directionality: guess of the mixing occurring in
OMs.
Molecular Orbital (MO) Theory
Diagram of molecular energy levels
Magnetic and spectral properties
Paramagnetic vs. Diamagnetic
Electronic transitions
Solid State - Conductance
Predicts existence of molecules
Bond Order
Molecular Orbital (MO) Theory
Two atomic orbitals combine to form
a bonding molecular orbital
an anti-bonding molecular orbital
e
-
in bonding MOs = stability
e
-
in anti-bonding MOs = instability
# atomic orbitals combined equals # of
molecular orbitals formed
Central Themes
Quantum mechanical level
Molecule viewed as a collection of nuclei
surrounded by delocalized molecular orbitals
Atomic wave functions are summed to obtain
molecular wave functions.
If wave functions reinforce each other, a bonding
MO is formed (region of high electron density
exists between the nuclei).
If wave functions cancel each other, an
antibonding MO is formed (a node of zero electron
density occurs between the nuclei).
An Analogy
Amplitudes of wave
functions added
Amplitudes of wave
functions subtracted.
MO: Molecular Hydrogen
The bonding MO is lower in energy than an AO
The anti- bonding MO is higher in energy than an AO
Considerations
Bond Order =1/2( # bonding e
-
# antibonding e
-
)

Higher bond order = stronger bond

Molecular electron configurations
Highest Occupied Molecular Orbital = HOMO
Lowest Unoccupied Molecular Orbital = LUMO

An Example: H
2
(
1s
)
2

MO: Molecular Hydrogen
Predicting Stability: H
2
+
& H
2
-



1s
AO of H
1s
AO of H
MO of H
2
+

bond order
= 1/2(1-0)
= 1/2
H
2
+
does exist
bond order
= 1/2(2-1)
= 1/2
H
2
-
does exist
1s


MO of H
2
-

1s
AO of H
AO of H
-

configuration is (
1s
)
1

configuration is
(
1s
)
2
(
1s
)
1

Helium: He
2
+
vs He
2

E
n
e
r
g
y

MO of
He
+

*
1s

1s

AO of
He
+

1s
MO of
He
2

AO of
He
1s
AO of
He
1s
*
1s

1s

E
n
e
r
g
y

He
2
+
bond order = 1/2
He
2
bond order = 0
AO of
He
1s
Bond Length vs. Bond Order
Next Row: 2s & 2p orbitals
*
2
s

2s

2s
1s
*
1
s

1s

*
1
s

1s

1s
2s
*
2
s

2s

Li
2
B.O. = 1 Be
2
B.O. = 0
Bonding in s-block
homonuclear
diatomic molecules.
E
n
e
r
g
y

Li
2

Be
2

Combinations for p-orbitals
Axial symmetry
means bond
Non-axial
symmetry
means bond

P orbital Complications
Results in one & one * MO
One pair from 2p
z


Results in two & two * MOs
One pair for 2p
x
and one pair for 2p
y


> half filled p orbitals (O, F, Ne)
energy
2p
< 2
2p
< 1*
2p
< 2*
2p


half filled p orbitals (B, C, N)
energy 2
2p
<
2p
< 2*
2p
< 1*
2p

MO Now with S & P
X 2
X 2
P orbital Complications
Results in one & one * MO
One pair from 2p
z


Results in two & two * MOs
One pair for 2p
x
and one pair for 2p
y


> half filled p orbitals (O, F, Ne)
energy
2p
< 2
2p
< 1*
2p
< 2*
2p


half filled p orbitals (B, C, N)
energy 2
2p
<
2p
< 2*
2p
< 1*
2p

S-P Energy Separation
E(2p)-E(2s):

N 12.4 eV
O 16.5 eV
F 31.6 eV
For N:
small 2p/2s separation
big
*
(2s) / (2pz) repulsion
S - P orbital mixing
Relative Energy Levels for 2s & 2p
MO energy levels
for O
2
, F
2
, and Ne
2

MO energy levels
for B
2
, C
2
, and N
2

WITHOUT big
2s-2p repulsion
WITH big 2s-2p
repulsion
Triumph for MO Theory?
Figure 9.37
Diagram of the
Kind of
Apparatus Used
to Measure the
Paramagnetism
of a Sample
Can MO Theory Explain Bonding?
SOLUTION:
PROBLEM: As the following data show, removing an electron from N
2
forms
an ion with a weaker, longer bond than in the parent molecules,
whereas the ion formed from O
2
has a stronger, shorter bond:
PLAN: Find the number of valence electrons for each species, draw the MO
diagrams, calculate bond orders, and then compare the results.
Explain these facts with diagrams that show the sequence and occupancy of MOs.
Bond energy (kJ/mol)
Bond length (pm)
N
2
N
2
+
O
2
O
2
+

945
110
498 841 623
112 121 112
N
2
has 10 valence electrons, so N
2
+
has 9.
O
2
has 12 valence electrons, so O
2
+
has 11.
Can MO Theory Explain Bonding?

2s

2s

2p

2p

2p

2p

N
2
N
2
+
O
2
O
2
+

bond
orders
1/2(8-2)=3 1/2(7-2)=2.5 1/2(8-4)=2

2s

2s

2p

2p

2p

2p

bonding e
-
lost
1/2(8-3)=2.5
antibonding
e
-
lost
Real World Applications
Most molecules are heteroatomic
What needs to be considered?
Orbitals involved
Electronegativity (Orbital energies)
Hybridization (Group Theory)
Mixing
Heteronuclear Diatomic Molecules
Molecular orbital diagrams for heteronuclear
molecules have skewed energies for the
combining atomic orbitals to take into account the
differing electronegativities.
The more electronegative elements are lower in
energy than those of the less electronegative
element.
Energy Level Diagram for NO
Heteronuclear Diatomic Molecules
The energy differences between bonding
orbitals depend on the electronegativity
differences between the two atoms
The larger the difference the more polar the bond
that is formed (ionic character increases)
The difference reflects the amount of overlap
between the bonding orbitals. If the difference is
too great the orbitals cannot overlap effectively
and nonbonding orbitals will be formed.
Formation of MOs in HF
The bond in HF involves the 1s electron of
H and the 2p orbital of F
A bonding and antibonding MO are produced

sp
and MOs
The remaining 2p orbitals on F have no overlap
with H orbitals. They are termed as
nonbonding orbitals. These orbitals retain the
characteristics of the F 2p atomic orbitals.
Lack of overlap to produce nonbonding
orbitals is much more pronounced for
side-on bonding

*
sp

The Energy Level Diagram for HF

Lets Start Slowly: HF
Valence electrons
H 1s
1

F 1s
2
2s
2
2p
5

Focus on the valence interactions
Accommodate for differences in
electronegativity
Allow mixing between symmetry-
allowed states

Lets Start Slowly: HF
E
n
e
r
g
y

MO
of HF
AO
of H
1
s

2p
x
2p
y

AO
of F
2p
E
n
e
r
g
y

The MO diagram for NO
MO of NO
2s
AO of N
2p
*
2s

2s

2s
AO of O
2p

2p

2p
*
2p
*
2s
N O
0 0
N O
-1 +1
possible Lewis
structures
Figure 9.39 The Molecular Orbtial Energy-Level
Diagrams, Bond Orders, Bond Energies, and Bond
Lengths for the Diatomic Molecules B
2
Through F
2
Figure 9.41
The Molecular
Orbital
Energy-Level
Diagram for
the NO
Molecule
Figure 9.42
The Molecular
Orbital
Energy-Level
Diagram for
Both the NO
+

and CN
-
ions
Figure 9.43 A Partial Molecular Orbital
Energy-Level Diagram for the HF Molecule
Figure 9.44 Electron Distribution
Figure 9.48 (a) The Molecular Orbital
System in Benzene is Formed by Combining
the six p Orbtials From the Six sp
2

Hybridized Carbon Atoms (b) The Electrons
in the Resulting pi Molecular Orbitals are
Delocalized Over the Entire Ring of Carbon
Atoms
Figure 9.48
Figure 9.49 (a) The p Orbitals Used to
Form the P Bonding System in the
NO
3
-
. (b) A Representation of the
Delocalization of the Electrons in the
Pie Molecular Orbital System of the
No
3
-
ion
Figure 9.49
Try this:
Generate an MO Diagram for CO
What is the bond order?
What is the HOMO?
highest occupied molecular orbital
What is the LUMO?
lowest unoccupied molecular orbital
Draw a corresponding Lewis dot structure
Bonus: Based on your answers above, what
can you envision for the bonding interaction
of CO with a transition metal (like Fe)?
HOMO is lone pair on C.
CO always binds to
metals via the C end
2 H
.

H:H
Energy Diagram
BENZENE PI MOLECULAR ORBITALS

6
six ps
six mos
top
view
etc
CYCLOPENTADIENYL ANION

5
CYCLOPENTADIENYL ANION