Anorganic Chemistry

Molecular Orbital Theory

Deta Rispa Dini
06111410015
Chemistry Education Study Program
Faculty Of Teacher and Training Education
Center
Sriwijaya University
2014

A.Introduction
B.Molecular Orbital Diagram
C.Molecular Orbitals Of Complexes
D.Conclusions
E.Video

A. Introduction
The goal of molecular orbital theory is to describe molecules
in a similar way to how we describe atoms, that is, in terms of
orbitals, orbital diagrams, and electron configurations.
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).
Molecular orbitals form when atomic orbitals with similar
energies and proper symmetry can overlap. Atomic orbitals
with differing energies or the wrong spatial orientation
(orthogonal) do not combine, and are called non-bonding
orbitals.

Molecular Orbital Theory

Constructively:
() or + = (1/2 ) [(1sa) +
(1sb) ]
Destructively:
(*) or - = (1/2 ) [(1sa) - (1sb)

MOLECULAR ORBITAL THEORY

The bonding
orbital results in
increased electron
density between
the two nuclei, and
is of lower energy
than the two
separate atomic
orbitals.

MOLECULAR ORBITAL THEORY

The bonding orbital
+
is sometimes given
the notation g,
where the g stands
+
for gerade, or
symmetric with
respect to a center
of inversion.
The signs on the molecular
orbitals
indicate the sign of the wave function, not
ionic charge.

MOLECULAR ORBITAL THEORY

The anti-bonding
+
orbital is
sometimes given
the notation u,
+
where the u stands
for ungerade, or
asymmetric with
respect to a center
The signs on the molecular
orbitals
of inversion.
indicate the sign of the wave function, not
ionic charge.

MOLECULAR ORBITAL DIAGRAM

This is a
molecular orbital
energy level
diagram for the p
orbitals. Note
that the
bonding orbital is
lowest in energy
due to the
greater overlap
end-on-end.

u
g
2p

u
g

2p

MOLECULAR ORBITAL DIAGRAM

The alternate
notation is
provided on the
right side of the
energy level
diagram.

u
g
2p

u
g

2p

MOLECULAR ORBITAL DIAGRAMS

1.

2.
3.

4.

Electrons preferentially occupy

molecular orbitals that are lower in
energy.
Molecular orbitals may be empty, or
contain one or two electrons.
If two electrons occupy the same
molecular orbital, they must be spin
paired.
When occupying degenerate
molecular orbitals, electrons occupy
separate orbitals with parallel spins

MOLECULAR ORBITAL DIAGRAMS

Although molecular orbitals form
from inner (core) electrons as well as
valence electrons, many molecular
orbital diagrams include only the
valence level.

MOLECULAR ORBITAL DIAGRAMS

For O2,
there will be a
total of 12
valence
electrons that
must be
placed in the
diagram.

MOLECULAR ORBITAL DIAGRAMS

2p

2s

2p

2s

For O2,
there will be a
total of 12
valence
electrons that
must be
placed in the
diagram.

MOLECULAR ORBITAL DIAGRAMS

2p

2s

2p

2s

For O2,
there will be a
total of 12
valence
electrons that
must be
placed in the
diagram.

MOLECULAR ORBITAL THEORY

Each line in the diagram represents

an orbital.
The molecular orbital volume
encompasses the whole molecule.
The electrons fill the molecular
orbitals of molecules like electrons fill
atomic orbitals in atoms

MOLECULAR ORBITAL THEORY

Electrons go into the lowest energy

orbital available to form lowest
potential energy for the molecule.
The maximum number of electrons in
each molecular orbital is two. (Pauli
exclusion principle)
One electron goes into orbitals of
equal energy, with parallel spin,
before they begin to pair up. (Hund's
Rule.)

MOLECULAR ORBITAL DIAGRAM

(H2)

http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/main.html

MO DIAGRAM FOR O2

http://www.chem.uncc.edu/faculty/murphy/1251/slides/C19b/sld
027.htm

MOLECULAR ORBITAL DIAGRAM

(HF)

http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/main.html

MOLECULAR ORBITAL DIAGRAM

(CH4)
So far, we have only look at molecules with
two atoms.
MO diagrams can also be used for larger
molecules.

http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/mai
n.html

MOLECULAR ORBITAL DIAGRAM

(H2O)

MOLECULAR ORBITALS OF
COMPLEXES
Group theory is also used to
construct molecular orbital diagrams
for the complexes of metal atoms or
ions. The symmetry combinations of
the atomic orbitals on the ligands are
determined, and then matched
with appropriate atomic orbitals on
the central metal. Both and
bonding between the metal and
ligands can be considered.

CONCLUSIONS

Bonding electrons are localized

between atoms (or are lone pairs).
Atomic orbitals overlap to form
bonds.
Two electrons of opposite spin can
occupy the overlapping orbitals.
Bonding increases the probability of
finding electrons in between atoms.
It is also possible for atoms to form
ionic and metallic bonds.

VIDEO