Molecular Orbital Theory

Edward A. Mottel
Department of Chemistry
Rose-Hulman Institute of Technology
 Bonding Theories
 Ionic Model
 Skeleton Diagrams
 Lewis Dot Diagrams
• Formal Charge, Resonance
 Molecular Orbital Theory
• Extends atomic orbitals concepts to
molecules

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 Bonding in Diatomic Molecules
Diatomic: molecule contains two atoms

••

•
•
••
A+ •• B •• •• C •• D ••
••

•
•
••
Ionic bonding Covalent bonding
large difference in small difference in
electronegativity electronegativity

Give an example of a compound with ionic bonding.

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 Homodiatomic Molecules
The best example of covalent bonding
involves homodiatomic molecules.
Contains two of the same type of atom.
•
•
••
•• A •• A ••
•
• e.g., H2, O2, F2, N2
••
Why are these molecules the best examples
of covalent bonding?

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 Heterodiatomic Molecules
HF, BN and CO are heterodiatomic molecules.

Contain two different atoms.

H-F
positive end negative end

These molecules are polar covalent.

What factors might help predict the positive

and negative ends of the molecule?
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 A Little Review

What is an orbital?

Give an example of an atomic orbital?

What is the name of the mathematical function

that determines the shape of an orbital?

What is the maximum number of electrons

that can be in one orbital?
 Molecular Orbitals
When two atoms come close to each other,
what happens to the orbitals of each atom?

a bond forms
1s atomic 1s atomic
orbital orbital
sb molecular
orbital
sigma s bonding molecular orbital
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 Molecular Orbitals

Orbital wave functions

can add & subtract to give
new wave functions and
corresponding
molecular orbitals (mo).
Atoms bond
together when
the wave functions
constructively overlap.
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 SIGMA BOND ()
A bond between two atoms in which the electron
density of the molecular orbital is between the
two nuclei is called a sigma bond.

nuclei

(sb)2 molecular
orbital

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 Molecular Orbitals (mo)
 Obey many of the same rules as atomic
orbitals (ao).
• two electrons per molecular orbital.
• specific regions of space.
• one molecular orbital formed for each
atomic orbital used.

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 Wave Functions
The amplitude (height) of each wavefunction
can either be positive or negative.

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 Wavefunctions
Bonding & Antibonding Orbitals

b

Constructively interfere in certain regions of space.

*

Destructively interfere in certain regions of space.

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 Bonding & Antibonding Orbitals
sb When a bonding
molecular orbital forms,
an antibonding
molecular orbital
H H also forms.

s*

Bonds form where orbitals overlap and electrons are.

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 Atomic and Molecular Orbitals
Atomic orbitals include
z
y
x
1s 2py 3dz2

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 Atomic and Molecular Orbitals
Molecular orbitals include
z

y
x
s b
x* z*

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 Atomic and Molecular Orbitals

This represents an orbital

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 Atomic and Molecular Orbitals
carbon: 1s2 2s2 2p2

energy

Orbitals An orbital can be empty

can have or can contain
different energies 1 or 2 electrons.
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 Molecular Orbital Diagrams
 Examples
• dihydrogen
• dihelium
• dihelium(I) ion

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 Dihydrogen, H2

H H
s*
energy

sb
H H
The branch lines indicate which Two 1s1 hydrogen orbitals
atomic orbitals are involved in overlap to form a sb
generating the molecular orbitals.
bonding molecular orbital
1s1 hydrogen orbital
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 Dihydrogen, H2
What advantage can
an orbital gain in forming
s* a molecular orbital from
energy

an atomic orbital?

H H
s
b

ao mo ao Dihydrogen is diamagnetic
(s )
b 2
and contains one bond
electronic configuration (one pair of bonding electrons).
of the hydrogen molecule.
Why is dihydrogen
diamagnetic?
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 Dihelium, He2
Two electrons occupy
s* the highest
Eachmolecular
helium atomorbital
energy

forming
has a s*
the electronic
configuration 1s2
Two (each contributes
electrons occupy
sb
the 2lowest
electrons to the helium
molecular orbital
molecular orbitals)
atomic orbital atomic orbital forming a  s
b

of one He atom of the other

He atom

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 Dihelium, He2

s* Why doesn’t He2 exist

energy

as a stable molecule?

The electronic configuration

 b
s of the dihelium molecule is
(sb)2 (s*)2

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 Dihelium(I) Ion, He2+

He He
s*
energy

He He+
sb

How many valence electrons must be considered

in the dihelium(I) ion?
Complete the molecular orbital diagram using the available electrons.
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 Dihelium(I) Ion, He2+
These represent
the atomic orbitals.
s*
energy

He He+
sb
Shaded means
2 electrons
Lined
means 1

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 Dihelium(I) Ion, He2+

s*
energy

He He+
sb

Draw an outline
Fill-in theof the molecular
molecular orbitals.
orbitals,
shaded for 2 electrons, lined for 1.

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 Dihelium(I) Ion, He2+

s* What physical properties

energy

are predicted for the

dihelium(I) ion?
sb (magnetic and bond order)

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 Orbitals Are Wave Functions
 Wave functions contain mathematical terms
that can have positive and negative values.
 An s orbital value can either be less than
zero or greater than zero.
 The two lobes of a p orbital are separated by
a node and have opposite signs.

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 Orbitals Are Wave Functions

Different colors represent

opposite mathematical signs.
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 Pi Bond Formation
y
A pi bond () occurs
when two lobes of each
atomic orbital overlap.
z

py- py Orbital Overlap

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 Pi Bond Formation
The molecular orbital
y does not lie directly on y
the internuclear axis.

z z

py- py Orbital Overlap Resulting Bonding

Molecular Orbital

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  Antibond Formation
 What is the symbol of a  antibond?
 How is a  antibond formed?
 What does a  antibond look like?
 Pi Antibond Formation
y y

z z

py- py Antibond Resulting Antibonding

Orbital Overlap Molecular Orbital

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 Pi Bonds

y* yb

y* bonding orbital yb bonding orbital

has four lobes and has two lobes and
holds a maximum holds a maximum
of two electrons. of two electrons.

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 Pi Bonding Involving Px Orbitals

x x
xb

Resulting Bonding
px- px Orbital Overlap Molecular Orbital

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 Pi Bonding Involving Px Orbitals

x x
x*

px- px Antibonding Resulting Antibonding

Orbital Overlap Molecular Orbital

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 Pi Bonding Involving p Orbitals

2p
px-px overlap gives  and x*
x
b

y
py-py overlap gives y and y*
b

From the mo diagram,

how can you determine that z
xb and yb x
are equally stable?
Why are xb and yb equally stable?
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 Molecular Orbital Diagrams
Involving s and p Orbitals

The molecular orbitals

formed depend on 2p
the atomic orbitals’

energy
overlap
direction 2s
energy
1s

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 Molecular Orbital Diagrams
Involving s and p Orbitals

Identify the orbitals

that represent the 2p
following

Nonbonding
Antibonding
Bonding
Pi bonds
Sigma molecular
molecular
andand
bonds
antibonds
orbitals 2s
antibonds

Weak pz-s mo interaction 1s

Homonuclear examples:
O2, F2
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 Diatomic Molecular Orbital Diagram
Strong pz-s interaction

Homonuclear
energy

2p Examples:
Li2, B2, C2, N2
Heteronuclear
2s Examples:
NO, BO, BO+,
CO, CO+,
1s CN, CN–

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 Homonuclear Diatomic Molecules
 Determine is the sequence of molecular
orbitals based on the strong pz-s interaction
diagram.
 Determine the bond order and magnetic
properties for homodiatomic molecules of the
first nine elements.
 Show the bond lengths are consistent with
these diagrams.

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 Orbital Sequence
(sn) (sb) (s*) (x,yb) (zb) (x,y*) (z*)
z*
x,y*
energy

2p
zb
x,yb
s*
2s sb

1s sn

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 Dinitrogen
Diberyllium
Dicarbon
Diboron (14
Dilithium(10
(12
(6 total
(8total
total
total ––e––)
eee )) )
Complete
Bondthe
Order
mo diagram
and Magnetic
for Li2Properties?
, Be2, B2, C2 or N2
z*
x,y*
2p
zb
x,yb
energy

s *
2s
First, sb Then,
fill in the fill in the
valence
1s sn mo diagram
electrons.

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 Compare the bond order, bond length and
magnetic properties of O2, O2+ , O2– and O22–
energy z*
x,y*
2p
x,yb
 zb
2s s*
O 2
–+
2–
sb
1.123
1.207
1.26 Å
1.49 Å
Å
properties?1s sn

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 Dioxygen

•• ••
•• ••
O •• •• O

What are the advantages and disadvantages

of this description of dioxygen?
 Compare the physical properties predicted for
Dioxygen by the Lewis Dot Diagram and MO Theory

•• ••
•• ••
O •• •• O

Bond Order Magnetic Properties

Lewis Dot
2 ? (diamagnetic)
Structure
Molecular paramagnetic
Orbital 2
Theory 2 unpaired electrons

Liquid dioxygen will cling to the pole of a magnet.

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 Compare the physical properties for the
Dioxygenyl(I) Ion, Dioxygen, Superoxide Ion and
Peroxide Ion
Bond Bond Magnetic
Length Order Properties
O2+ 1.123 Å 2.5 paramagnetic (1)
O2 1.207 2 paramagnetic (2)
O2– 1.26 1.5 paramagnetic (1)
O22– 1.49 1 diamagnetic

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 Oxygen-Oxygen Bonds

•• ••
•• ••

••
••
O O H O O H

••
••
Which oxygen-oxygen bond is easier to break?
 Difluorine
Dineon (20(18total
totalee))
––

Bond Order and Magnetic Properties?

energy z*
x,y*
2p
x,yb
 zb
2s s*
sb
1s sn

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 Homodiatomic Molecules
bond
bond
length magnetic
Electronic Configuration order properties
(Å)
H2 (sb)2 1 0.74 diamagnetic

He2 (sb)2 (s*)2 0

Li2 (sn)4 (sb)2 1 2.67 diamagnetic

Be2 (sn)4 (sb)2 (s*)2 0

B2 (sn)4 (sb)2 (s*)2 (xb)1 (yb)1 1 1.59 paramagnetic

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 Homodiatomic Molecules
Electronic Configuration

C2 (sn)4 (sb)2 (s*)2 (x,yb)4

N2 (sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2

O2 (sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2 (x*)1 (y*)1

F2 (sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2 (x,y*)4
Ne2 (sn)4 (sb)2 (s*)2 (x,yb)4 (zb)2 (x,y*)4 (z*)2

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 Homodiatomic Molecules
bond bond magnetic
order length (Å) properties
C2 2 1.31 diamagnetic

N2 3 1.10 diamagnetic

O2 2 1.207 paramagnetic

F2 1 1.42 diamagnetic

Ne2 0

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