Molecular Orbital Theory

Table of Contents
1. 1. Introduction
2. 2. Principles of Molecular Orbital Theory
3. 3. Sigma Bonds
1. 3.1. Pi Bonds
4. 4. Determining Bond Order
5. 5. Determining the Stability of the Molecule
6. 6. Outside links
7. 7. References
8. 8. Problems
9. 9. Solutions
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. 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.

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. Take a hydrogen molecule (H
2
) for example. It has two molecular
orbitals, an antibonding orbital and a bonding orbital. Compared to the original atomic orbitals,
a bonding molecular orbital has lower energy and is therefore more stable. 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. Due to the lower potential energy in molecular bonds than in separate atomic orbitals, it
is more energy efficient for the electrons to stay in a molecular bond rather than be pushed back
into the 1s orbitals of separate atoms. This is what keeps bonds from breaking apart. A bonding
orbital can only be formed if the orbitals of the constituent atoms have the same phase (here
represented by colors). The wave functions of electrons of the same phase interfere
constructively which leads to bonding.

Principle Details/Examples
1
Total number of molecular orbits
is equal to the total number of
atomic orbitals from combining
atoms

The molecule H
2
is composed of two H atoms. Both
H atoms have a 1s orbital, so when bonded together, there
are therefore two molecular orbitals.

2 Bonding molecular orbitals have Bonding molecular orbitals help stabilize a system of atoms
If the atomic orbitals have the different phases, they interfere destructively and an antibonding
molecular orbital is formed (see the top part of the figure below). Antibonding molecular orbitals
have a higher energy than the atomic orbitals of their constituent atoms. When antibonds are
formed, the interaction creates a decrease in the intensity of the negative charge, which causes a
decrease in the plus minus attraction in the molecular bond. This smaller attraction leads to the
higher potential energy. This type of bond destabilizes the attraction between atoms, so the
number of antibonding orbitals in a molecule must be less than the number of bonding orbitals.

less energy than the constituent
atomic orbitals before bonding
Antibonding molecular orbitals
have more energy than the
constituent atomic orbitals before
bonding.

since less energy is associated with bonded atoms as
opposed to a system of unbound atoms.
Likewise, antibonding molecular orbitals cause a system to
be unstabilized since more energy is associated with bonded
atoms than that of a system of unbound atoms.
3
Following both the Pauli
exclusion principle and Hund's
rule, electrons fill in orbitals of
increasing energy.

Electrons fill orbitals with the lowest energy first. No more
than 2 electrons can occupy 1 molecular orbital at a time.
Furthermore, all orbitals at an energy level must be filled
with one electron before they can be paired. (see second
diagram below)
4
Molecular orbitals are best formed
when composed of Atomic
orbitals of like energies.

Molecular Orbital Configuration of Li
2
:
(
1s
)
2
(
*
1s
)
2
(
2s
)
2

The bonding (
1s
)
2
and antibonding (
*
1s
)
2
cancel each other out, leaving (
2s
)
2

as the valence electrons involved in the atoms' bonding.

Sigma Bonds
Molecular orbitals that are symmetrical about the axis of the bond are called sigma molecular
orbitals, often abbreviated by the Greek letter . The diagram to the left shows the 1s orbitals of
2 Hydrogen atoms forming a sigma orbital. 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 end to end 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 is a representation of the energy levels of the bonding and antibonding
orbitals formed in the hydrogen molecule. Two molecular orbitals were formed, one
antibonding (*) and one bonding ().The two electrons in the hydrogen molecule have
antiparallel spins. Notice that the * orbital is empty and has a higher energy than the orbital.

Sigma bonding orbitals and antibonding orbitals can also be formed between p orbitals (shown
below). 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.




Pi Bonds
The pi bonding bonds as a side to side overlap, which then causes there to be no electron density
along the axis, but there is density above and belong the axis. The diagram below shows a pi
antibonding molecular orbital and a pi bonding molecular orbital.


2p
y
Orbitals

The two 2p
y
atomic orbitals overlap parallely to form two pi molecular orbitals which are
asymmetrical about the axis of the bond.
2p
z
orbitals

The two 2p
z
orbitals overlap to create another pair of pi 2p and pi *2p molecular orbitals. The
2p
z
-2p
z
overlap is similar to the 2p
y
-2p
y
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
y
-2p
y
overlap.
Drawing Molecular Orbital Diagrams
Determine the number of electrons in the molecule.
Fill the molecular orbitals from bottom to top until all the electrons are added. Describe
the electrons with arrows. Put two arrows in each molecular orbital, with the first arrow
pointing up and the second pointing down.
Orbitals of equal energy are half filled with parallel spin before they begin to pair up.
Determining Bond Order
Bond Order indicates the strength of the bond. The higher the Bond Order, the stronger the
bond.
Bond Order= 1/2(a-b)
where a is the number of e
-
in bonding Molecular Orbitals and b is the number of e
-
in
antibondng Molecular Orbitals.
Determining the Stability of the Molecule
If the Bond Order is Zero, then no bonds are produced and the molecule is not stable (for
example He
2
). If the Bond Order is 1, then it is a single covalent bond. The higher the Bond
Order, the more stable the molecule is. An advantage of Molecular Orbital Theory when it comes
to Bond Order is that it can more accurately describe partial bonds (for example in H
2
+
, where
the Bond Order=1/2), than Lewis Structures.
Outside links
http://en.wikipedia.org/wiki/Molecular_Orbital_Theory
http://www.youtube.com/watch?v=8PiL-ceRHZQ
http://www.youtube.com/watch?v=nCMZavJhzkU
http://www.meta-synthesis.com/webboo...diatomics.html
References
1. 1. Petrucci, RH et al. (2007). General Chemistry: Principles and Modern Applications.
New Jersey: Pearson Prentice Hall.
2. 2. Dingrando, Laurel, Kathleen Tallman, Nicholas Hainen, and Cheryl Wistrom.
Chemistry. Glencoe/McGraw-Hill School Pub Co, 2004.
3. Kotz, John C., Paul M. Treichel, and Gabriela C. Weaver. "Bonding and Molecular
Structure:Orbital Hybridization and Molecular Orbitals." Chemistry & Chemical
Reactivity. Belmont, CA: Thomson Brooks/Cole, 2006. 457-66. Print.