Molecular Orbital

Theory
 Atomic Orbitals
 Heisenberg Uncertainty Principle states that it is
impossible to define what time and where an
electron is and where is it going next. This makes it
impossible to know exactly where an electron is
traveling in an atom.
 Since it is impossible to know where an electron is at
a certain time, a series of calculations are used to
approximate the volume and time in which the
electron can be located. These regions are called
Atomic Orbitals. These are also known as the
quantum states of the electrons.
 Only two electrons can occupy one orbital and they
must have different spin states, ½ spin and – ½ spin
(easily visualized as opposite spin states).
 Orbitals are grouped into subshells.
 This field of study is called quantum mechanics.
 Atomic Subshells
 These are some examples of atomic orbitals:
 S subshell: (Spherical shape) There is one S orbital in
an s subshell. The electrons can be located anywhere
within the sphere centered at the atom’s nucleus.

http://www.chm.davidson.edu/ronutt/che115/AO.htm

 P Orbitals: (Shaped like two balloons tied together) There

are 3 orbitals in a p subshell that are denoted as px, py,
and pz orbitals. These are higher in energy than the
corresponding s orbitals.

http://www.chm.davidson.edu/ronutt/che115/AO.htm
 Atomic Subshells (cont’d)

 D Orbitals: The d subshell is divided into 5 orbitals (d

( xy , dxz , dyz ,
dz2 and dx2-y 2). These orbitals have a very complex shape and
are higher in energy than the s and p orbitals.
Molecular Orbital Theory

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.
Forming a Covalent Bond

 Molecules can form bonds by sharing electron

 Two shared electrons form a single bond
 Atoms can share one, two or three pairs of
electrons
 forming single, double and triple bonds
 Other types of bonds are formed by charged
atoms (ionic) and metal atoms (metallic).
 Atomic and Molecular
Orbitals (cont’d)
 Orbital Mixing
 When atoms share electrons to form a bond, their
atomic orbitals mix to form molecular bonds. In
order for these orbitals to mix they must:
 Have similar energy levels.
 Overlap well.
 Be close together.

This is and example of orbital

mixing. The two atoms share
one electron each from there
outer shell. In this case both 1s
orbitals overlap and share their
valence electrons.

http://library.thinkquest.org/27819/ch2_2.shtml
Energy Diagram of Sigma
Bond Formation by Orbital
Overlap
sp3 Hybrid atomic
orbitals
sp2 Hybrid atomic
orbitals
sp Hybrid atomic orbitals
Multiple bonds with VB
Multiple bonds with VB
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.)
 Diatomic Molecular

Orbital
In the case of Theory
diatomic molecules, the interactions are easy to
see and may be thought of as arising from the constructive
interference of the electron waves (orbitals) on two different
atoms, producing a bonding molecular orbital, and the
destructive interference of the electron waves, producing an
antibonding molecular orbital
•This Approach is called LCAO-MO
(Linear Combination of Atomic Orbitals to Produce
Molecular Orbitals)

A Little Math is need to

understand

Only a Little I promise!

 Atomic and Molecular
Orbitals
 In atoms, electrons occupy atomic orbitals, but in
molecules they occupy similar molecular orbitals which
surround the molecule.
 The two 1s atomic orbitals combine to form two molecular
orbitals, one bonding (σ ) and one antibonding (σ *).

• This is an
illustration of
molecular orbital
diagram of H2.one
• Notice that
electron from each
atom is being
“shared” to form a
covalent bond. This is
an example of orbital
http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/main.html
mixing.
The He “dimer”
Examples of Sigma Bond
Formation
Molecular Orbital
Diagram (H2)

http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/main.html
Molecular Orbitals from
p A.O.s

NOTE: Symmetry is important in forming M.O. from A.O.s (LCAO)

Molecular Orbitals from
p A.O.s
MO Diagram for O2

http://www.chem.uncc.edu/faculty/murphy/1251/slides/C19b/sld027.htm
 M.O.s from O2

σ 1s
σ ∗
1s σ σ ∗
2s
2s

σ 2p π π ∗
2p
2p
Electron configurations
for diatoms
Molecular Orbital
Diagram (HF)

http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/main.html
Energy Levels in HF
This diagram shows the allowed
energy levels of
2p
1s ↑
Isolated H (1s1) and F (1s22s22p5) ↑↓ ↑↓ ↑↓ ↑↓ ↑
atoms and, between them, the HF ↑↓
molecule.
↑↓ ↑↓
2s
Note: Valence MOs
1. F 1s is at much lower energy than H
1s (because of the higher nuclear
charge)

2. F 1s2 electrons are core electrons.

Their energy does not change when HF
is formed.

3. H 1s and F 2p valence electrons go ↑↓ ↑↓

into molecular orbitals with new
energies.
H HF F
 Molecular Orbitals in HF
This non-bonding
molecular orbital (n) has 2p
1s ↑
an almost spherical lobe ↑↓ ↑↓ ↑↓ ↑↓ ↑
showing only slight
delocalisation between ↑↓
the two nuclei. ↑↓ n ↑↓
Non-bonding orbitals 2s
look only slightly different
to atomic orbitals, and
have almost the same
energy.

This core orbital is

almost unchanged
from the F 1s orbital.
↑↓ n ↑↓
The electrons are H F
bound tightly to the F
nucleus. H HF F
Molecular Orbitals in HF This (empty) LUMO is an
antibonding orbital with a
node on the interatomic
axis between H and F.
These two degenerate (filled) HOMO’s are
centred on the F atom, like 2px and 2py orbitals. σ∗
2p
1s ↑ n n
↑↓ ↑↓ ↑↓ ↑↓ ↑
↑↓ σ
↑↓ n ↑↓
Electrons in these two orbitals are not
shared (much) by the fluorine nucleus. They
behave like the 2p orbitals and are also non-
bonding (n).

This MO, which is is like a 2pz

orbital, is lower in energy in
the molecule (a bonding
orbital), and one lobe is
delocalised around the H atom.
↑↓ n ↑↓

H HF F
 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/main.html
Molecular Orbital Diagram
(H2O)
 Molecular Orbital Theory
Diatomic molecules: The bonding in F2
The second set of combinations with π symmetry (orthogonal to the first set):

This produces an MO over

+ the molecule with a node on
the bond between the F

≡
atoms. This is thus a
2pxA 2pxB bonding MO of π u symmetry.

π u = √ 0.5 (2pxA + 2pxB )

This produces an MO around

- both F atoms that has two
≡

nodes: one on the bond axis

and one perpendicular to the
2pxA 2pxB bond. This is thus an
antibonding MO of π g
π g* = √ 0.5 (2pxA - 2pxBsymmetry.
)
 Molecular Orbital Theory
MO diagram for F2
You will typically see the
F F2 F
diagrams drawn in this way.
3σ * The diagram is only showing the
u
MO’s derived from the valence
electrons because the pair of
MO’s from the 1s orbitals are
1π *
g much lower in energy and can
be ignored.
2p (px,py)
pz Although the atomic 2p orbitals
2p are drawn like this:
Energy

1π u they are actually all the same

energy and could be drawn like
this:
3σ g at least for two non-interacting F
atoms.
Notice that there is no mixing of
2σ u * AO’s of the same symmetry
from a single F atom because
2s 2s there is a sufficient difference in
energy between the 2s and 2p
2σ g
orbitals in F.
 Molecular Orbital Theory
MO diagram for F2
F F2 F
Another key feature of such
LUMO 3σ u * diagrams is that the π -type
MO’s formed by the
combinations of the px and py
HOMO 1π * orbitals make degenerate sets
g
(i.e. they are identical in energy).
2p (px,py)
pz
2p
The highest occupied molecular
Energy

1π u
orbitals (HOMOs) are the 1π g*
pair - these correspond to some
of the “lone pair” orbitals in the
3σ g
molecule and this is where F2
will react as an electron donor.

2σ u * The lowest unoccupied

molecular orbital (LUMO) is the
2s 2s 3σ u* orbital - this is where F2
2σ g will react as an electron
 Molecular Orbital Theory
MO diagram for B2
B B2 B In the MO diagram for B2, there
several differences from that of
3σ u * F2. Most importantly, the
ordering of the orbitals is
changed because of mixing
between the 2s and 2pz orbitals.
1π *
g From Quantum mechanics: the
(px,py)
closer in energy a given set of
2p
pz orbitals of the same symmetry,
2p
the larger the amount of mixing
Energy

LUMO 3σ g
that will happen between them.
This mixing changes the
energies of the MO’s that are
HOMO 1π u produced.
The highest occupied molecular
2σ u * orbitals (HOMOs) are the 1π u
2s 2s pair. Because the pair of orbitals
is degenerate and there are only
2σ g
two electrons to fill, them, each
MO is filled by only one electron
- remember Hund’s rule.
 Molecular Orbital Theory
Diatomic molecules: MO diagrams for Li2 to F2
Remember that the separation between
the ns and np orbitals increases with
increasing atomic number. This means
that as we go across the 2nd row of the
periodic table, the amount of mixing
decreases until there is no longer enough
mixing to affect the ordering; this happens
at O2. At O2 the ordering of the 3σ g and
the 1π u MO’s changes.
As we go to increasing atomic number,
the effective nuclear charge (and
electronegativity) of the atoms increases.
This is why the energies of the analogous
orbitals decrease from Li2 to F2.
In this diagram, 2s-2pz mixing The trends in bond lengths and
the labels are
for the valence energies can be understood from the size
shell only - they Molecule Li Be B2 C N2 O2 F2 Ne
ignore the 1s
of2 each2atom, the2 bond order and by 2
shell. They Bond Order 1 0
examining 1the orbitals
2 3 that2 are filled.
1 0
should really Bond Length (Å) 2.67 n/a 1.59 1.24 1.01 1.21 1.42 n/a
start at 2σ g and
2σ u*. Bond Energy (kJ/mol) 105 n/a 289 609 941 494 155 n/a
Diamagnetic (d)/ Paramagnetic (p) d n/a p d d p d n/a
More complicated
molecules
 Modern MO
calculations

W. Kohn J. A. Pople
(1923-) (1925-2004)

Nobel prize in Chemistry

1998
 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.
 References
 http://www.chemguide.co.uk/atoms/properties/atomor
 http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/main.html
 http://en.wikipedia.org/wiki/Molecular_orbital_theory
 http://library.thinkquest.org/27819/ch2_2.shtml