Sigma and Pi bonding and
Molecular Orbital Theory
Valence Bond Theory
• Hybridization is a major player in this
approach to bonding.
• There are two ways orbitals can overlap to
form bonds between atoms.
Sigma () Bonds
• Sigma bonds are characterized by
– Head-to-head overlap.
– Cylindrical symmetry of electron density about the
internuclear axis.
Pi () Bonds
• Pi bonds are
characterized by
– Side-to-side overlap.
– Electron density above
and below the
internuclear axis.
Single Bonds
Single bonds are always bonds, because
overlap is greater, resulting in a stronger bond and
more energy lowering.
Multiple Bonds
In a multiple bond one of the bonds is a bond
and the rest are bonds.
Multiple Bonds
• In a molecule like
formaldehyde (shown
at left) an sp2 orbital
on carbon overlaps in
fashion with the
corresponding orbital
on the oxygen.
• The unhybridized p
orbitals overlap in
fashion.
Multiple Bonds
In triple bonds, as in
acetylene, two sp
orbitals form a
bond between the
carbons, and two
pairs of p orbitals
overlap in fashion
to form the two
bonds.
Delocalized Electrons:
Resonance
When writing Lewis structures for species like the
nitrate ion, we draw resonance structures to more
accurately reflect the structure of the molecule or
ion.
Delocalized Electrons:
Resonance
• In reality, each of the four
atoms in the nitrate ion has a
p orbital.
• The p orbitals on all three
oxygens overlap with the p
orbital on the central nitrogen.
Delocalized Electrons:
Resonance
This means the electrons are
not localized between the
nitrogen and one of the
oxygens, but rather are
delocalized throughout the ion.
Resonance
The organic molecule
benzene has six
bonds and a p orbital on
each carbon atom.
Resonance
• In reality the electrons in benzene are not
localized, but delocalized.
• The even distribution of the electrons in benzene
makes the molecule unusually stable.
Molecular Orbital (MO) Theory
Though valence bond
theory effectively conveys
most observed properties
of ions and molecules,
there are some concepts
better represented by
molecular orbitals.
Molecular Orbital (MO) Theory
• In MO theory, we
invoke the wave nature
of electrons.
• If waves interact
constructively, the
resulting orbital is lower
in energy: a bonding
molecular orbital.
Molecular Orbital (MO) Theory
If waves interact
destructively, the
resulting orbital is
higher in energy: an
antibonding molecular
orbital.
MO Theory
• In H2 the two electrons
go into the bonding
molecular orbital.
• The bond order is one
half the difference
between the number of
bonding and antibonding
electrons.
MO Theory
For hydrogen, with two
electrons in the bonding
MO and none in the
antibonding MO, the
bond order is
1
(2 - 0) = 1
2
MO Theory
• In the case of He2, the
bond order would be
1
(2 - 2) = 0
2
• Therefore, He2
does not exist.
MO Theory
• For atoms with both s
and p orbitals, there are
two types of
interactions:
– The s and the p orbitals
that face each other
overlap in fashion.
– The other two sets of p
orbitals overlap in
fashion.
MO Theory
• The resulting MO
diagram looks like this.
• There are both and
bonding molecular
orbitals and * and *
antibonding molecular
orbitals.
MO Theory
• The smaller p-block elements in
the second period have a
sizeable interaction between the
s and p orbitals.
• This flips the order of the and
molecular orbitals in these
elements.
Second-Row MO Diagrams
