Valence Bond Theory vs.

Molecular orbital theory (15 min)

Molecular Orbital Theory

Introduction video ( ~10 min)

https://www.youtube.com/watch?v=UNcAoFzy6N0
(15 minutes)
Nitrogen, N2

Electrons end up being all paired – so nitrogen

should be diamagnetic and repel magnetic fields.
Let’s take a look at oxygen, O2

Electrons are also all paired – so oxygen should

be diamagnetic and repel magnetic fields.

Are they?
Experimentally O2 is paramagnetic and valence bond
theory fails to explain this. Oxygen isn’t the only
molecule.

Therefore a new theory was put forth:

Molecular Orbital Theory

Resonance is another example of the limitations of

valence bond theory. Bond lengths and strengths
are intermediate between single, double or triple
bonds. Molecular orbital theory is often a
better approach to use with molecules that have
extended π systems.
In valence bond theory we localized
one electron to each atom

In molecular orbital theory each electron moves

over the whole molecule
 Recall that electrons move as waves.
In Molecular Orbital Theory, the orbitals in a
molecule arise from the overlap of atomic
orbitals that satisfy two criteria:

• The orbitals have

compatible symmetry

• The orbitals are similar

in energy
The interactions of the atomic orbitals to form
molecular orbitals is represented by an energy
diagram called a molecular orbital diagram.

The diagram displays the orbitals arranged vertically

from lowest to highest energy.

The atomic orbitals for the various atoms are listed in

columns at the left and right sides of the diagram.
The molecular orbitals are listed in a column down
the center of the diagram.
The atomic orbitals are given the usual s, px, etc.
designation.

The molecular orbitals, which are often identified by

their symmetry properties, may also be identified by
their bonding properties: σ, σ*, π, π*.
(* = antibonding)
The number of molecular orbitals = the number of
atomic orbitals combined.

The strength of the bond depends upon the degree

of orbital overlap.
Each orbital accommodates two electrons. As a result of
the formation of H2 molecule, the energy of the system is
lowered and become more stable.

Molecular
orbital
diagram:

Bond order = ½ [(bonding electrons) – (antibonding electrons)]

Bond order is a measure of the number of chemical bonds
 Consider He2:

The bond
order
calculation
shows that
there will be a
bond order of
zero.

The amount of stabilization due to bonding is equal to the

amount of destabilization due to anti-bonding, because there
are two electrons in the bonding orbital and two electrons in
the anti-bonding orbital. Therefore, there is no net stabilization
due to bonding so the He2 molecule will not exist.
What happens when we move into bonding between
elements that have electrons in their p orbitals?
Looking at O2
1. Which statement is false? A sigma molecular orbital

(a) may result from overlap of p atomic orbitals

perpendicular to the molecular axis (side-on).

(b) may result from overlap of p atomic orbitals along the

molecular axis (head-on).

(c) may result from overlap of two s atomic orbitals.

(d) may result from overlap of one s and one p atomic

orbitals.

(e) may be either bonding or antibonding.

1. Which statement is false? A sigma molecular orbital

(a) may result from overlap of p atomic orbitals

perpendicular to the molecular axis (side-on).

(b) may result from overlap of p atomic orbitals along the

molecular axis (head-on).

(c) may result from overlap of two s atomic orbitals.

(d) may result from overlap of one s and one p atomic

orbitals.

(e) may be either bonding or antibonding.

2. Carbon monoxide has ten bonding electrons and four
antibonding electrons. Therefore it has a bond order
of

(a) 3
(b) 7
(c) 1
(d) 5/2
(e) 2
2. Carbon monoxide has ten bonding electrons and four
antibonding electrons. Therefore it has a bond order
of
(a) 3
(b) 7
(c) 1
(d) 5/2
(e) 2
3. Which of the following is the correct electron
configuration for C2?

(a) 1s2 2s2 2py2 *1s2 *2s2 *2py2

(b) 1s2 *1s2 2s2 *2s2 2py2 *2pz1 2p1

(c) 1s2 *1s2 2s2 *2s2 2py2 2pz2

(d) 1s2 *1s2 2s2 *2s2 2py1 2pz1

(e) 1s2 *1s2 2s2 *2s2 2py1 *2py1 2pz1 *2pz1

3. Which of the following is the correct electron
configuration for C2?

(a) 1s2 2s2 2py2 *1s2 *2s2 *2py2

(b) 1s2 *1s2 2s2 *2s2 2py2 *2pz1 2p1

(c) 1s2 *1s2 2s2 *2s2 2py2 2pz2

(d) 1s2 *1s2 2s2 *2s2 2py1 2pz1

(e) 1s2 *1s2 2s2 *2s2 2py1 *2py1 2pz1 *2pz1

4. What is the correct electron configuration for the
molecular ion, B2+?

(a) 1s2 *1s2 2s2 *2s2 2p2

(b) 1s2 *1s2 2s2 *2s2 2py2

(c) 1s2 *1s2 2s2 *2s2 2py2 2pz1

(d) 1s2 *1s2 2s2 *2s2 2p1 2py1

(e) none of the above.

4. What is the correct electron configuration for the
molecular ion, B2+?

(a) 1s2 *1s2 2s2 *2s2 2p2

(b) 1s2 *1s2 2s2 *2s2 2py2

(c) 1s2 *1s2 2s2 *2s2 2py2 2pz1

(d) 1s2 *1s2 2s2 *2s2 2p1 2py1

(e) none of the above.

5. Draw the molecular orbital diagram for the molecular
ion, N2+. The number of electrons in the 2p molecular
orbital is:

(a) 0
(b) 1
(c) 2
(d) 3
(e) 4
5. Draw the molecular orbital diagram for the molecular
ion, N2+. The number of electrons in the 2p molecular
orbital is:

(a) 0
(b) 1
(c) 2
(d) 3
(e) 4
6. What is the bond order in O2+?

(a) 3.5
(b) 2.0
(c) 1.5
(d) 2.5
(e) 0
6. What is the bond order in O2+?

(a) 3.5
(b) 2.0
(c) 1.5
(d) 2.5
(e) 0
7. Draw the molecular orbital diagram for B2. The
number of unpaired electrons in the B2 molecule is
_____.

(a) zero
(b) 1
(c) 2
(d) 3
(e) 4
7. Draw the molecular orbital diagram for B2. The
number of unpaired electrons in the B2 molecule is
_____.

(a) zero
(b) 1
(c) 2
(d) 3
(e) 4
8. Which one of the following statements is false?
(a) Valence bond theory and molecular orbital theory can be
described as two different views of the same thing.
(b) When one considers the molecular orbitals resulting from
the overlap of any two specific atomic orbitals, the
bonding orbitals are always lower in energy than the
antibonding orbitals.
(c) Molecular orbitals are generally described as being more
delocalized than hybridized atomic orbitals.
(d) One of the shortcomings of molecular orbital theory is its
inability to account for a triple bond in the nitrogen
molecule, N2.
(e) One of the shortcomings of valence bond theory is its
inability to account for the paramagnetism of the oxygen
molecule, O2.
8. Which one of the following statements is false?
(a) Valence bond theory and molecular orbital theory can be
described as two different views of the same thing.
(b) When one considers the molecular orbitals resulting from
the overlap of any two specific atomic orbitals, the
bonding orbitals are always lower in energy than the
antibonding orbitals.
(c) Molecular orbitals are generally described as being more
delocalized than hybridized atomic orbitals.
(d) One of the shortcomings of molecular orbital theory is its
inability to account for a triple bond in the nitrogen
molecule, N2.
(e) One of the shortcomings of valence bond theory is its
inability to account for the paramagnetism of the oxygen
molecule, O2.
9. Antibonding molecular orbitals are produced
by
(a) constructive interaction of atomic orbitals.
(b) destructive interaction of atomic orbitals.
(c) the overlap of the atomic orbitals of two
negative ions
(d) all of these
(e) none of these
9. Antibonding molecular orbitals are produced
by
(a) constructive interaction of atomic orbitals.
(b) destructive interaction of atomic orbitals.
(c) the overlap of the atomic orbitals of two
negative ions
(d) all of these
(e) none of these