Molecular Orbitals

Molecular Orbitals
Molecular orbitals result from the combination of
atomic orbitals.
Since orbitals are wave functions, they can combine
either constructively (forming a bonding molecular
orbital), or destructively (forming an antibonding
molecular orbital).
Overlap of Two 1s Atomic Orbitals
Two MO’s are formed when the two atomic orbitals
overlap
 The in-phase combination produces a 1s molecular
bonding orbital.
Has lower energy than corresponding AO’s
 The out-of-phase contribution produces a molecular
antibonding orbital
Has higher energy than corresponding AO’s
 1*s
Formation of Molecular Orbitals
Bonding orbital – the wave funtions are in-phase
and overlap constructively (they add).
 Bonding orbital’s are lower in energy than AOs
Anti-bonding orbital – the wave functions are out-
of-phase and overlap destructively (they subtract)
 Anti-bonding orbital’s are higher in energy than the
AO’s
When two atomic orbital’s combine, one bonding and
one anti-bonding MO is formed.
The signs on the molecular orbitals indicate the
sign of the wave function, not ionic charge.
Molecular Orbital Diagrams
1. Electrons preferentially occupy molecular orbitals
that are lower in energy.
2. Molecular orbitals may be empty, or contain one or
two electrons.
3. If two electrons occupy the same molecular orbital,
they must be spin paired.
4. When occupying degenerate molecular orbitals,
electrons occupy separate orbitals with parallel spins
before pairing.
Bond Order
Bond order is an indicator of the bond strength and
length. A bond order of 1 is equivalent to a single
bond. Fractional bond orders are possible.

The bond order of the molecule =

(# e- in bonding orbtls) - (# e- in anti-bonding
orbtls)
2 2
Sigma and Pi bonding and
Molecular Orbital Theory
 What do we take from all this?
Three simple kinds of molecular orbitals

1. Sigma (bonding) orbitals (s).

Electrons delocalised along the axis between two nuclei.
These may be represented as shared electrons, e.g. H:H or
H:F; H-H or H-F
2. Non-bonding orbitals (n)
Orbitals that are essentially unchanged from atomic orbitals, and remain
localised on a single atom (unshared).
These may be represented as a pair of electrons on one atom.

3. Sigma star (anti-bonding) orbitals (s*)

Orbitals with a node or nodes along the axis between two
nuclei. These do not contribute to bonding, they “undo”
bonding.
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.
Examples of Sigma Bond Formation
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.
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 s and p
bonding molecular
orbitals and s* 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
Electronic Configurations – Box Diagram

http://wine1.sb.fsu.edu/chm1045/notes/Struct/EConfig/Struct08.htm

 The two electrons in Helium represent the complete filling of

the first electronic shell. Thus, the electrons in He are in a very
stable configuration
 For Boron (5 electrons) the 5th electron must be placed in a 2p
orbital because the 2s orbital is filled. Because the 2p orbitals
are equal energy, it doesn't matter which 2p orbital is filled.