The Molecular Orbital Theory, initially developed by Robert S.

Mullikan, incorporates the wave like characteristics of electrons in describing bonding

behavior. In Molecular Orbital Theory, the bonding between atoms is described as a combination of their atomic orbitals. While the Valence Bond
Theory and Lewis Structures sufficiently explain simple models, the Molecular Orbital Theory provides answers to more complex questions. In the
Molecular Orbital Theory, the electrons are delocalized. Electrons are considered delocalized when they are not assigned to a particular atom or bond
(as in the case with Lewis Structures). Instead, the electrons are smeared out across the molecule. The Molecular Orbital Theory allows one to
predict the distribution of electrons in a molecule which in turn can help predict molecular properties such as shape, magnetism, and Bond Order.
Introduction
Atoms form bonds by sharing electrons. Atoms can share two, four, or six electrons, forming single, double, and triple bonds respectively. Although it is
impossible to determine the exact position of an electron, it is possible to calculate the probability that one will find the electron at any point around the
nucleus using the Schrdinger Equation. This equation can help predict and determine the energy and spatial distribution of the electron, as well as the
shape of each orbital. The figure below shows the first five solutions to the equation in a three dimensional space for a one electron atom. The colors
show the phase of the function. In this diagram, blue stands for negative and red stands for positive. Note, however, that the 2s orbital has 2 phases,
one of which is not visible because it is inside the other.

Figure 1: Cartoons of the volume occupied by electrons in the 1s, 2s, and 2p hydrogen-like orbitals.
Principles of Molecular Orbital Theory
In molecules, atomic orbitals combine to form molecular orbitals which surround the molecule. Similar to atomic orbitals, molecular orbitals are wave
functions giving the probability of finding an electron in certain regions of a molecule. Each molecular orbital can only have 2 electrons, each with an
opposite spin. Each molecular orbital can only have 2 electrons, each with an opposite spin. Once you have the molecular orbitals and their energy
ordering the ground state configuration is found by applying the Pauli principle, the aufbau principle and Hund's rule just as with atoms.
The principles to apply when forming pictorial molecular orbitals from atomic orbitals are summarized in the table below:
Figure
shows

2
how

Principle

antibonding
Total number of molecular orbitals is equal to the total number
be formed by of atomic orbitals used to make them.
orbitals
in(bonding,
Bonding molecular orbitals are lower energy than the atomic
out-of-phase orbitals from which they were formed.
top). If the
orbitals
with

are
the

Details/Examples

orbitals can
The molecule H2 is composed of two H atoms. Both H atoms have a
1s orbital, so when bonded together, there are therefore two combining s
molecular orbitals.
phase
bottom) and
Electrons in bonding molecular orbitals help stabilize a system of
atoms since less energy is associated with bonded atoms as opposed (antibonding,
to a system of unbound atoms. Bonding orbitals are formed by inatomic
phase combinations of atomic orbitals and increase the electron
combined
density between the atoms (see figure 2 below)
same phase

they interfere Antibonding molecular orbitals are higherenergy than the

atomic orbitals from which they were formed.
and
a
orbital
Bonding

is

orbitals have
than
the
orbitals from
were formed.
of the energy
to
the

constructively
bonding

Electrons in antibonding molecular orbitals cause a system to be

destabilized since more energy is associated with bonded atoms than formed.
that of a system of unbound atoms. Antibonding orbitals are formed molecular
by out-of-phase combinations of atomic orbitals and decrease the
lower energy
electron density between atoms (see figure 2 below).
atomic
Following both the Pauli exclusion principle andHund's rule, Electrons fill orbitals with the lowest energy first. No more than 2 which
they
electrons fill in orbitals of increasing energy.
electrons can occupy 1 molecular orbital at a time. Furthermore, all
orbitals at an energy level must be filled with one electron before they The lowering
can be paired. (see figure 3 below)
is attributed

Molecular orbitals are best formed when composed of Atomic When Li2 forms the two lowest energy orbitals are the pair of bonding
of orbitals of like energies.
and antibonding orbitals formed from the two possible combinations
of the 1s on each atom. The 2s orbitals combine primarily with each
other to form another pair of bonding and antibonding orbitals at a
the increase
higher energy.
density
shielding
repulsion

(below)
bonding and

increase

in

the nuclear
because of
in
electron
between the

nuclei. If the
atomic
orbitals are combined with different phases, they interfere destructively and an antibonding molecular orbital is formed. Antibonding molecular orbitals
have a higher energy than the atomic orbitals from which they were formed. The higher energy is attributed to the reduced shielding of the nuclear
repulsion because of the lower electron probability density between the nuclei.

Figure 2: Combining hydrogen-like s orbitals to generate bonding (bottom) and antibonding (top) orbitals. The dark dot represents the location of the
nucleus. Note the decrease in electron density between the nuclei in the antibonding orbital.
Bonds
Molecular orbitals that are symmetrical about the axis of the bond are called sigma molecular orbitals, often abbreviated by the Greek letter . Figure 2
shows the 1s orbitals of 2 Hydrogen atoms forming sigma orbitals. There are two types of sigma orbitals formed, antibonding sigma orbitals
(abbreviated ), and bonding sigma orbitals (abbreviated ). In sigma bonding orbitals, the in phase atomic orbitals overlap causing an increase in
electron density along the bond axis. Where the atomic orbitals overlap, there is an increase in electron density and therefore an increase in the
intensity of the negative charge. This increase in negative charge causes the nuclei to be drawn closer together. In sigma antibonding orbitals ( ), the
out of phase 1s orbitals interfere destructively which

results in a low electron density between the nuclei

as seen on the top of the diagram.

The diagram below (figure 3) is a representation of the
formed in the hydrogen molecule. Two molecular

energy levels of the bonding and antibonding orbitals

orbitals were formed: one antibonding () and one

bonding ().The two electrons in the hydrogen

the orbital is empty and has a higher energy than

molecule have
the orbital.

antiparallel

spins.

Notice

that

Figure 3: An MO energy level diagram for H2. The up

or spin down.

and down arrows represent electrons that are spin up

Sigma bonding orbitals and antibonding orbitals can

also be formed between p orbitals (figure 4). Notice

that the orbitals have to be in phase in
order to form bonding orbitals. Sigma
molecular orbitals formed by p orbitals
are often differentiated from other types
of sigma orbitals by adding the subscript p below it. So the antibonding orbital shown in the

diagram below would be *p.

Figure 4: The formation of a bonding and antibonding orbital using p-orbitals.

Bonds
The bonding is a side to side overlap of orbitals, which then causes there to be no electron density along the axis, but there is density above and
below the axis. The diagram below (figure 5) shows a antibonding molecular orbital and a bonding molecular orbital.

Figure 5: The side on overlap of p orbitals to form pi bonding and antibonding orbitals. Note that there is a second set of p orbitals sticking in and out of
the image that can combine in the same way. (see cartoons immediately below)
2py Orbitals
The two 2py atomic orbitals overlap in parallel to form two molecular
orbitals which are asymmetrical about the axis of the bond.
2pz orbitals
The

two

2pz orbitals
overlap to create
another pair of pi
2p and pi *2p
molecular
orbitals. The 2pz-2pz overlap is similar to the 2py-2py overlap because it is just the orbitals
of the 2pz rotated 90 degrees about the axis. The new molecular orbitals have the same
potential energies as those from the 2p y2py overlap.
In summary the three pairs of p orbitals

can combine to form one set of \sigma\ orbitals

and two sets of \pi\ orbitals.

Drawing

Molecular

Orbital

Diagrams

1.

2.

3.
4.

Determine how many valence

can ignore the core electrons as core

electrons you have on each atom (you

orbitals contribute little to molecular

orbitals). This gives you the total number

among the molecular orbitals you form.

of electrons you will have to distribute

For example consider B2 (each atom has

an electron configuration of [He]2s22p),

Draw a cartoon energy level

which has a total of 6 valence electrons.

diagram with lines for the valence atomic

energy levels (orbitals) of each atom. Put

the right. Include the electrons. Leave

one atom's levels on the left and one on

space in the middle for your molecular

energy levels (orbitals). It can help to

well. Shown for diboron immediately

include cartoons of the atomic orbitals as

below.

Combine each pair of orbitals

of similar energy in-phase and out-of-

phase to create molecular orbitals as shown for diboron in the figure following step 4.
Move the electrons from the atoms into the molecule to determine the molecular electron configuration as shown immediately below
Note that the and orbitals formed from the p's are not always in the order energy less than energy. For first row diatomics the ordering shown
above is valid for Z 7. Thus for oxygen and fluorine the is below the orbitals.
Bond Orders and Stability of Molecules
Bond Order indicates the strength of the bond with the greater the bond order, the stronger the bond.
Bond Order=0.5(ab)

Problems
1.

What is the molecular orbital diagram for for the diatomic hydrogen molecule, H 2? How stable is the molecule? Is it diamagnetic or

2.

paramagnetic?
What is the molecular orbital diagram for the diatomic helium molecule, He 2? How stable is the molecule? Diamagnetic or paramagnetic?

3.
4.

What is the molecular orbital diagram for the diatomic oxygen molecule, O 2? How stable is the molecule? Diamagnetic or paramagnetic?
What is the molecular orbital diagram for the diatomic neon molecule, Ne 2? How stable is the molecule? Diamagnetic or paramagnetic?

5.

What is the molecular orbital diagram for the diatomic fluorine molecule, F 2? How stable is the molecule? Diamagnetic or paramagnetic?

Solutions
1. The molecular orbital diagram for a diatomic hydrogen molecule, H2, is

Bond Order = 1/2(2 - 0) = 1

The bond order above zero, so H2 is stable.
Because there are no unpaired electrons, H 2 is diamagnetic.
2. The molecular orbital diagram for a diatomic helium molecule, He2, shows the following.

Bond Order = 1/2(2 - 2) = 0

bond order is zero so molecule is unstable.
would be diamagnetic.
3. The molecular orbital diagram for a diatomic oxygen molecule, O 2, is

Bond Order = 1/2(10 - 6) = 2

The bond order is two so the molecule is stable.
There are two unpaired electrons, so molecule is paramagnetic.
4.The molecular orbital diagram for a diatomic Neon molecule, Ne 2, is

Bond Order = 1/2(10 - 10) = 0

bond order is zero, so Ne2 is unstable.
diamagnetic

5. The molecular orbital diagram for the diatomic fluorine molecule, F 2 is B.O. = 1/2(10 - 8) = 1. B.O is one so the fluorine molecule is stable.Because
all of the electrons are paired, F2 is diamagnetic.