Chapter 9

Molecular Orbitals

1
Chapter Outline

1. Molecular Orbitals
2. Molecular Orbital Energy Level
Diagrams
3. Bond Order and Bond Stability
4. Homonuclear Diatomic Molecules
5. Heteronuclear Diatomic Molecules
6. Delocalization and the Shapes of
Molecular Orbitals
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Molecular Orbital Theory
Combination of atomic orbitals on different atoms forms
molecular orbitals (MOs) so that electrons in MOs belong
to the molecule as a whole.
Waves that describe atomic orbitals have both positive
and negative phases or amplitudes.
As MOs are formed the phases can interact constructively
or destructively.

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Molecular Orbitals
There are two simple types of molecular
orbitals that can be produced by the overlap
of atomic orbitals.
1. Head-on overlap of atomic orbitals produces
(sigma) orbitals.
2. Side-on overlap of atomic orbitals produces (pi)
orbitals.
Two 1s atomic orbitals that overlap produce
two molecular orbitals designated as:
1s or bonding molecular orbital
1s* or antibonding molecular orbital.

4
Molecular Orbitals

Graphically these two orbitals look like

this:

5
Molecular Orbitals

Energetically, the molecular orbitals split.

1. The 1s lies lower in energy.
2. The 1s* is higher in energy.

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Molecular Orbitals
The head-on overlap of two corresponding p atomic
orbitals on different atoms, say 2p x with 2px produces:
1. 2p x bonding orbital
2.
* 2p x antibonding orbital

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Molecular Orbitals

Graphically, these orbitals look like this:

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Molecular Orbitals

Side-on overlap of two corresponding

p atomic orbitals on different atoms
(say 2py with 2py or 2pz with 2pz)
produces:
2p 2p
y z

1. or (both are bonding orbitals)

* 2p y * 2p z
2. or (both are nonbonding
orbitals)

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Molecular Orbitals

Graphically these orbitals look like this:

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Molecular Orbital Energy
Level Diagram
Now that we have seen what these MOs
look like and a little of their energetics,
how are the orbitals filled with electrons?
Order of filling of MOs obeys same rules
as for atomic orbitals.
Including
1. Aufbau principle
2. Hunds Rule
Thus the following energy level diagram
results for the homonuclear diatomic
molecules H2 through N2.
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Molecular Orbital Energy
Level Diagram

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Bond Order and Bond
Stability
Once the energy level diagram has been filled
with the appropriate number of electrons, how do
we determine the molecular stability?
Bond order (bo) of a molecule is defined as half
the number of electrons in bonding orbitals
minus half the number of electrons in
antibonding orbitals

bo =
#e -

in bonding orbitals # e - in antibondin g orbitals
2

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Bond Order and Bond
Stability
The larger the bond order, the more stable the
molecule or ion is.
Bond order = 0 implies there are equal
numbers of electrons in bonding and
antibonding orbitals.
~ same stability as separate atoms
Bond order > 0 implies there are more
electrons in bonding than antibonding orbitals.
Molecule is more stable than separate atoms.
The greater the bond order, the shorter the
bond length and the greater the bond energy.
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Homonuclear Diatomic
Molecules
Consider the overlap of the
atomic orbitals of two nitrogen
atoms to form an N2 molecule.
Each N atom has 7 electrons thus
the N2 molecule has 14 electrons.
Obey the Aufbau principle and
Hunds rule to place the 14 electrons
in the energy level diagram.

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Homonuclear Diatomic
Molecules

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Homonuclear Diatomic
Molecules
In shorthand notation we represent this
configuration as

N2 2
1s
*2
1s
2
2s
*2
2s 2
2 py *2
2 py 2
2p

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Homonuclear Diatomic
Molecules
The greater the bond order of a bond the
more stable we predict it to be.
For N2 the bond order is
10 - 4
bo
2
6

2
3 correspond ing to a triple
bond in VB theory 18
 Homonuclear Diatomic
Molecules
MO treatment can also be applied to ions.
Ions are charged and that charge affects the
stability as well as the bond order.
Example 9-1: Write out the electron
configuration of the N2+ ion in abbreviated
notation ( s2 s*2). What is the bond order?
You do it!

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 Homonuclear Diatomic
Molecules
Example 9-1: Write out the electron
configuration of the N 2+ ion in abbreviated
notation ( s2 s*2). What is the bond
order?

N
+
2
2
1s
*2
1s
2
2s
*2
2s
2
2 py *2
2 pz 1
2 px

-
total of 13 e
9-4
bo = 2 12
2 20
 Homonuclear Diatomic
Molecules
Example 9-2: Write out the electron
configuration of the O2 molecule in
abbreviated notation. What is the bond order?
Is the molecule paramagnetic or diamagnetic?

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 Homonuclear Diatomic
Molecules
Example 9-2: Write out the electron
configuration of the O2 molecule in
abbreviated notation. What is the bond order?
Is the molecule paramagnetic or diamagnetic?
O2
2
1s
*2
1s
2
2s
*2
2s
2
2 px 2
2 py 2
2 pz *1
2 py *1
2 pz

10 - 6
bo = 2
2

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 Homonuclear Diatomic
Molecules
Example 9-2: Write out the electron
configuration of the O2 molecule in
abbreviated notation. What is the bond order?
Is the molecule paramagnetic or diamagnetic?
O 2 1s2 1s*2 2s2 2s*2 22 p x 22 p y 22 pz 2*1p y 2*1pz
10 - 6
bo = 2
2
2 unpaired e- paramagnet ic
Valence Bond theory predicts that O 2 is diamagneti c
experiment ally - O2 is paramagnet ic 23
 Homonuclear Diatomic
Molecules
Example 9-3: Write out the electron
configuration of the Be2 molecule in
abbreviated notation. What is the bond order?
Would you predict that the molecule exists?
You do it!

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 Homonuclear Diatomic
Molecules
Example 9-3: Write out the electron
configuration of the Be2 molecule in
abbreviated notation. What is the bond order?
Would you predict that the molecule exists?

Be 2
2
1s
*2
1s
2
2s
*2
2s

4-4
bo = 0
2
Since it has a bond order of 0,
Be 2 is not expected to exist. 25
 Homonuclear Diatomic
Molecules
Example 9-4: Write out the electron
configuration for F2. In this molecule the p
molecular orbital is lower than the p
molecular orbitals. What is the bond order?
Is F2 paramagnetic?
F2
2
1s
*2
1s
2
2s
*2
2s
2
2 px 2
2 py 2
2 pz *2
2 py *2
2 pz

10 - 8
bo = 1
2
No unpaired e diamagneti c
-
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 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.
Use HF as an example.

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 Heteronuclear Diatomic
Molecules ____

*
sp

1s

nonbonding orbitals




2p 2p

bonding orbitals
sp

4-2
bond order 1


2
2s 2s

nonbonding orbitals



1s 1s

H H-F F
atomic molecular atomic
orbital orbitals orbitals 28
Delocalization and Shapes
of Molecular Orbitals
Valence bond theory discusses
resonance formulas.
Carbonate ion (CO32-) is an example.

2- 2- 2-
O O O
C C C
O O O O O O

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Delocalization and Shapes
of Molecular Orbitals
Molecular orbital theory describes
shapes in terms of delocalization of
electrons.
Again carbonate ion (CO32-) is a good example.

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Delocalization and Shapes
of Molecular Orbitals
Molecular orbital theory describes
shapes in terms of delocalization of
electrons.
Again carbonate ion (CO32-) is a good example.

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Delocalization and Shapes
of Molecular Orbitals
The structure of benzene is described well
by molecular orbital theory.

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Delocalization and Shapes
of Molecular Orbitals
Resonance structure - VB theory.

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Delocalization and Shapes
of Molecular Orbitals
Molecular orbital theory

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Delocalization and Shapes
of Molecular Orbitals
Molecular orbital theory

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 Synthesis Question
Shown below are three electron density plots of
benzene. In these pictures, regions of high
electron density are red colored and regions of low
electron density are blue colored. Use these plots
to answer these questions.
Is benzene more susceptible to nucleophilic attack
(chemical species that are seeking positive
charges) or electrophilic attack (chemical species
that are seeking negative charges)?

36
 Synthesis Question
In benzene, which atoms are more likely
to react, C or H?

Electron density maps map with atoms

visible

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 Synthesis Question

Benzene is most susceptible to

electrophilic attack because the electrons
in the MOs are so accessible.
The H atoms are easily replaced on
benzene because they extend out beyond
the ring of delocalized electrons in
benzenes MO.

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 Group Question

Shown below are three electron density

plots of nitrobenzene. Use these plots to
answer these questions.
O
N
O

H C H
C C
Is nitrobenzene more
C C
susceptible to nucleo
H
attack (chemical species seeking positive
H C
H
charges) or electrophilic
nitrobenzene attack (chemical
species seeking negative charges)?

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 Group Question
In nitrobenzene, which atoms are more
likely to react, C, H, N or O?
Electron density maps map with atoms
visible

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End of Chapter 9
Molecular Orbital Theory is the basis of all
molecular modeling programs.
Fibrin - blood clotting enzyme

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