CHEM. 2AP UNIT 7 CH.

9 Covalent Bonding: Orbitals 48

MOLECULAR ORBITAL THEORY

• The localized electron model does an excellent job of predicting and justifying molecular shapes (VSEPR). It does
not deal with molecules with unpaired electrons and does not explain resonance. It also neglects bond energies.
• The Molecular Orbital Model allows an explanation of resonance and helps explain molecules with unpaired
electrons.
• It uses an arrangement of appropriately placed atomic nuclei and places electrons in molecular orbitals in a way
that lead to an energetically favorable stable molecule.
• Like the quantum mechanical model, the molecular orbital model utilizes orbitals and the filling of those orbitals
by electrons in a certain order of filling. Molecular orbitals have many of the same characteristics as atomic
orbitals. One of the most important is that they can hold two electrons with opposite spins. Molecular orbitals are
associated with the entire molecule.
• The molecular orbital model is used to explain molecules whereas atomic orbitals described atoms.
• Molecular orbitals are mathematical equations that describe the regions in a molecule where there is a high
probability of finding electrons in atoms. One way to derive molecular orbitals is by an appropriate combination of
the atomic orbitals of the atoms being united into a molecule.

• Molecular orbitals are formed from the combination of the orbitals of the atoms. One combination leads to a
bonding molecular orbital which is at a lower energy level than the separate atomic orbitals and has a high
electron probability or electron charge density between the bonded atoms.
• The other combination leads to an antibonding molecular orbital that is at a higher energy level than the separate
atomic orbitals and places a high electron probability away from the region between the bonded atoms. We use an
asterisk (*) to designate an antibonding orbital.
• Electrons in bonding molecular orbitals contribute to the strength of a bond between atoms.
• Electrons in antibonding molecular orbitals detract from the strength of the bond.

• The number of molecular orbitals formed is equal to the number of atomic orbitals that are combined.
When two atomic orbitals are combined, one of the resulting MOs is at a lower energy than the original atomic
orbitals; this is a bonding orbital. The other MO is at a higher energy than the original atomic orbitals; this is an
antibonding orbital.
• Electrons in bonding MOs tend to stabilize a molecule; electrons in antibonding MOs tend to destabilize a
molecule.

KEY IDEAS OF THE MO THEORY

• All the valence electrons in a molecule exist in a set of molecular orbitals of a given energy. The valence electrons
of each atom are not acting independently, but rather act with other valence electrons to form a set of MO’s.
• There are bonding and antibonding MOs. Bonding results in lower energy than if no interaction occurred.
Antibonding results in higher energy.
• A molecule will be stable if there is more bonding than antibonding interaction.
• Bond order (BO) is a measure of net bonding interactions.
# bonding electrons - # antibonding electrons
BOND ORDER =
2
• BO must be greater than 0 for a stable molecule to form.
• The higher the BO, the stronger the bond.

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 CHEM. 2AP UNIT 7 CH. 9 Covalent Bonding: Orbitals 49

• Note: A bond order equal to zero means that the molecule has equal numbers of electrons in bonding MOs (more
stable than in separate atoms) and in antibonding MO’s (less stable than in separate atoms). Such a molecule
would be no more stable than separate atoms, so it would not exist. A bond order greater than zero means that
more electrons occupy bonding MOs (stabilizing) than antibonding MO’s (destabilizing). Such a molecule would
be more stable than the separate atoms and we predict that its existence is possible.

USING THE MOLECULAR ORBITAL THEORY

THE HYDROGEN MOLECULE H2

*
The overlap of the 1s orbitals of 2 hydrogen atoms produces δ 1s and δ 1s molecular
orbitals. The 2 electrons of the molecule occupy the lower energy δ 1s orbital.

Because the 2 electrons in an H2 molecule are in a bonding orbital, the bond order is one.
We conclude that the H2 molecule would be stable and we know it is. The energy
associated with the 2 electrons in the H2 molecule is lower than that associated with the
same 2 electrons in separate 1s atomic orbitals. The lower the energy of a system the
more stable it is. As the energy of a system decreases, its stability increases.
Molecular orbital electron configuration of H2: ( δ 1s )2

**NOTE: Molecular electron configurations can be written in much the same way
as atomic (electron) configurations.
Orbitals are conserved. The number of molecular orbitals will always be the same as the number of atomic
orbitals used to construct them.

PROBLEMS: Use the MO theory to describe the bonding and stability of the H2- ion and the He2 molecule
(hypothetical). Give the electron configuration of each.

To help you solve this problem, I have included the MO energy-level diagrams of each below:

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 CHEM. 2AP UNIT 7 CH. 9 Covalent Bonding: Orbitals 50

BONDING IN HOMONUCLEAR DIATOMIC MOLECULES

You will now be able to describe the bonding in homonuclear diatomic molecules with regard to:
• Stability
• Bond order, relative bond energy and bond length
• Paramagnetism or diamagnetism

In the previous examples you used the MO model to assess the stability of diatomic molecules with 1s orbitals. In this
section we will expand the discussion to diatomic molecules containing 2s and 2p orbitals. Bonds can be formed when
atomic orbitals overlap in space. This is not possible with the 1s orbitals in period 2 elements because each of the
orbitals is too close to its own nucleus (therefore no overlap). Only the 2s and 2p orbitals (containing the valence
electrons) can participate in bond formation.

Sigma bonds (δ bonds) form between nuclear centers and these MO’s can be formed using 2s orbitals or 2px orbitals.
In addition, pi orbitals (π orbitals) cam be formed by the overlap of both 2py or 2pz orbitals. Also δ and π antibonding
orbitals exist. (See the diagram below).

PARAMAGNETISM AND DIAMAGNETISM

Paramagnetism and diamagnetism cam be proven using the relative positions of MO energy levels. Paramagnetism
indicates unpaired electrons in a substance. This causes the substance to be attracted to a magnetic field. Diamagnetism
indicates paired electrons in a substance. This causes the substance to be repelled from the magnetic field.

This property will be included in MO theory and using electron configuration to determine the stability of a diatomic
molecule. (see next)

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 CHEM. 2AP UNIT 7 CH. 9 Covalent Bonding: Orbitals 51

ELECTRON CONFIGURATIONS- The molecular energy-level diagram below shows the molecular orbitals
formed from atomic orbitals. Like the quantum mechanical model, the order of filling is from lower energy to higher
energy. (See exceptions to this order below)

Note: This is for the homonuclear elements of period 2 up to and including nitrogen N2, After N2, O2, F2, and
Ne2 (hypothetical) have a different filling order and configuration as shown below.

For period 2 diatomic molecules up to and including N2:

Electron configuration: δ2s δ *2s π2p δ2p π *2 p δ *2 p
For period 2 diatomic molecules O2, F2, and Ne2 (hypothetical): π2p and δ2p change order.
Electron configuration: δ2s δ *2s δ2p π2p π *2 p δ *2 p

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 CHEM. 2AP UNIT 7 CH. 9 Covalent Bonding: Orbitals 52

PRACTICE WITH THE MO MODEL

DO THIS:

For the molecule and ion: O2, O2-, and O22-:

• Draw the MO energy-level diagram.
• Give the electron configuration.
• Determine the bond order.
• Describe the relative bond energies.
• Describe the magnetism.

BONDING IN HETERONUCLEAR ATOMS

The MO model for homonuclear molecules works well for describing the bonding in atoms adjacent to one another on
the periodic table. The model is still valid for describing atoms which are next to each other but breaks down
with two very different atoms.

Ex: Draw the MO energy level diagram for the NO molecule. Determine its bond order, stability, and
magnetism.

DO ASSIGNMENT #2 AND #3 ON ASSIGNMENT SHEET

#2 P443-446 #1, 2, 7, 8, 9, 34, 35
#3 P446-447 #36, 38, 40, 42, 44, 49, 50, 51, 55

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