Presentation Outline

• Types of Molecular Orbital

MOLECULAR • Homonuclear Diatomic Molecules

ORBITAL • Heteronuclear Diatomic Molecules

• Bond Order

DR AMALINA MOHD TAJUDDIN

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Lewis structure, Valence Bond Theory & Hybridization The Central Themes of MO Theory

A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular orbitals.

Problems????? Atomic wave functions are summed to obtain molecular wave

functions.

• No direct info on bond energies If wave functions reinforce each other, a bonding MO is formed
• Assuming all electron are localized (stay one place) (region of high electron density exists between the nuclei).
• Not effective for unpaired electron
If wave functions cancel each other, an antibonding MO is formed
(a node of zero electron density occurs between the nuclei).

Erwin Schrodinger (1887-1961)

Discovery: Schrödinger’s wave equation

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 Substracting the wave function from each other
Formation of Molecular Orbitals
(Destructive Interference)
Constructive Interference
• Antibonding MO - a region of zero electron
• Adding the wave function together
density (a node) between the nuclei
• Bonding MO - a region of high electron • Substractive each other overlap
density between the nuclei
to light cancelling

An analogy
between light
Amplitudes of
waves and
wave functions
atomic wave subtracted.
functions.
Amplitudes of wave
functions added

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Energy and shape of H2 in molecular orbitals

Definition/ Similar Contours and energies of the bonding and antibonding

molecular orbitals (MOs) in H2.

• Bonding = constructive = addition

• Nonbonding = destructive = substraction antibonding antibonding MO is

higher in energy
than the AOs that
* Node - a region of an orbital where the probability of combined to form
them.
finding the electron is zero.

The bonding MO is lower in energy

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 Molecular Orbital (MO) Configurations Energy of H2 in molecular
orbitals
1. The number of molecular orbitals (MOs) formed is always
σ* antibonding MO σ Bonding MO
equal to the number of atomic orbitals combined.
Ø Has node between nuclei Ø Atom spread between
2. The more stable the bonding MO, the less stable the Ø e- density outside nuclei
corresponding antibonding MO. Aufbau internuclear region Ø Nuclei attracted to the
3. The filling of MOs proceeds from low to high energies. Ø e- do not shield nucleus, intervening e-
increases of nucleus to Ø e- being delocalized its
4. Each MO can accommodate up to two electrons. Pauli
repulsion. make charge
5. Use Hund’s rule when adding electrons to MOs of the antibonding MO higher E Ø e- repulsion reducing make
same energy. Ø Molecules less stable MO lower E
6. The number of electrons in the MOs is equal to the sum of when its empty Ø Molecules more stable than
all the electrons on the bonding atoms. separate atoms

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Number of Number of
Molecular Orbital (MO) Configurations
bond order =
1
2 ( electrons in
bonding
MOs
- electrons in
antibonding
MOs
)
• σ, σ*, π and π*
• ns, np
• E.g.: H2 : (σ1s)2 (σ*1s)0

• Exercise: He2, Li2

bond
order ½ 1 ½ 0

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 The MO diagram for H2 MO diagram for He2+ and He2

Filling molecular orbitals with electrons follows the

same concept as filling atomic orbitals.

s*1s s*1s

Energy
s*1s

Energy
Energy 1s 1s 1s
1s

1s 1s

H2 bond order s1s s1s

= 1/2(2 − 0) = 1 AO of MO of AO of AO of MO of AO of
s1s He He2+ He+ He He2 He
AO MO AO
of H of H2 of H He2 bond order = 0
He2+ bond order = 1/2

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SAMPLE PROBLEM 11.3 Predicting Stability of Species Using MO Diagrams

PROBLEM: Use MO diagrams to predict whether H2+ and H2- exist.

Determine their bond orders and electron configurations.

PLAN: Use H2 as a model and accommodate the number of electrons in

bonding and antibonding orbitals. Find the bond order.

SOLUTION:
bond bond Electron configuration?
order = order =
1/2(1-0) = 1/2(2-1) =
s* s*
1/2 H + does 1/2 H - does
2 2
exist exist Exist?

1s 1s 1s 1s

AO of H AO of H AO of H-
AO of H
s s configuration
configuration is (s1s)1 is (s1s)2(s*1s)1
MO of H2+ MO of H2-

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 Bonding in the s-block homonuclear diatomic molecules.
HOMONUCLEAR DIATOMIC MOLECULES

• Bonding in the s-block homonuclear diatomic molecules

• MO from Atomic p-orbital combination s*2s

Energy
s*2s

• Bonding in the p-block homonuclear diatomic molecules 2s 2s 2s

2s

s2s s2s

Li2 Be2

Li2 bond order = 1 Be2 bond order = 0

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MO from atomic p-orbital combinations

Orders of Energy Level
• Shapes and energy of MOs form from
combination • 2s are lower energy than 2p
• End to end - pair of s MOs, s2p, s*2p, • Bonding MOs lower than antibonding MOs
• Side to side - pair of p MOs, p2p and p*2p - end to end, than side to side
• Bonding MOs has greater electron density • Energy order:
between nuclei s2p < p2p < p*2p < s*2p
• Antibonding MOs has node between the nuclei, • s* higher energy because destabilizing effect
their electron density outside internuclear region greater than p*

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 Contours and energies of s and p MOs through Interaction between two equivalent p orbitals and the
Figure 11.19
combinations of 2p atomic orbitals. corresponding molecular orbitals

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Second-period Homonuclear Diatomic Second-period Homonuclear Diatomic

Molecules O2, F2, and Ne2 Molecules B2, C2 and N2

• Orbitals do not mix • Orbitals do mix because

because size atoms are size atoms are larger
small
• AOs are half filled, relative
• Relative strong repulsion small repulsion makes 2s
raise energy of 2p orbital and 2p orbital much closer,
high enough to minimize orbital mix occur
orbital mix

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 Figure 11.20 Relative MO energy levels for Period 2 homonuclear
diatomic molecules
without 2s-2p with 2s-2p
mixing mixing

2py, 2pz

2px

MO energy levels MO energy levels

for O2, F2, and Ne2 for B2, C2, and N2

HOMO AND LUMO

MO energy levels for O2,
F2, and Ne2 without 2s-2p
Energy order
[email protected]
s2p < p2p < p*2p < s*2p mixing

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2px

2py, 2pz
Bonding in the p-block element
2px • Higher bond order, the greater bond energy, shorter
bond length
2py, 2pz

• Paramagnetic - unpaired electron

- attracted to the magnetic field
• Diamagnetic - paired electron
- unaffected by the magnetic field

HOMO AND LUMO

MO energy levels
for B2, C2, and N2 with 2s-2p
mixing

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 Sample Problem 11.4 Using MO Theory to Explain Bond Properties

N2 N2+ O2 O2+
s*2p s*2p antibonding
e− lost

Figure 11.21 p*2p p*2p

MO occupancy
bonding
and molecular e− lost
s2p p2p
properties for B2
through Ne2 p2p s2p

s*2s s*2s

s2s s2s
1/2(8 − 2) = 3 1/2(7 − 2) = 2.5 BOND 1/2(8 − 4) = 2 1/2(8 − 3) = 2.5
ORDERS
Bond Energy = Bond Energy = Bond Energy = Bond Energy =
945 kJ/mol 841 kJ/mol 498 kJ/mol 623 kJ/mol

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vLewis diagram shows O2 is diamagnetic

No unpaired electrons

vMOs shows 2 electron unpaired

Experiments show O2 is paramagnetic
vParamagnetic /parallel

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 The MO diagram for HF

HETERONUCLEAR DIATOMIC MOLECULES s*

• Bonding HF

Energy
1s

• Bonding NO
• Bonding CO 2py 2pz 2p

s
AO MO of AO
of H HF of F

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s*2p The MO diagram for NO s*2p The MO diagram for CO

p*2p p*2p

2p 2p
s2p 2p s2p 2p
possible Lewis
structures possible Lewis
Energy

Energy
p2p 0 0 p2p structure

N O
s*2s s*2s
-1 +1
2s N O 2s
2s 2s
AO of N AO of O AO of C AO of O
s2s Bond Order? s2s Bond Order?
MO of NO MO of CO

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 MO in Benzene MO in Ozone
Lewis structure of ozone
Ø MO Theory structure of delocalized σ
and π bonding and antibonding MOs
Delocalized p orbitals
ØEach carbon sp2 hybridization: six σ
bonds between C-C and six σ bonds
between C-H
Ø Electron density of the pi (π) bond
delocalized over the entire molecules Ø π bond formed between sp orbital
of each O in O3
Ø An unhybridized 2p orbital on each
carbon atom overlap and form π bond. Ø The π electron delocalized
Ø The atom distribution on the p throughout the entire molecule
electron in benzene makes the
molecules unusually stable. Ø The bond length between O-O is
σ bonds in benzene
not single bond or double bond but
in between single and double bonds

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Example Solution From Table 10.5 we can deduce the properties of

ions generated from the homonuclear diatomic molecules.
The ion can be prepared by bombarding the N2 molecule
with fast-moving electrons. (a) Because has one fewer electron than N2, its electron
configuration is
Predict the following properties of :

(a) electron configuration

(b) The bond order of is found by using Equation (10.2):
(b) bond order
bond order = ½ (9 − 4) = 2.5

(c) magnetic properties (c) has one unpaired electron, so it is paramagnetic.

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 Exercise 1)

•
Sketch and name the resultant molecular orbitals for bonding and
antibonding complete with notation.
2px and 2px

1) Sketch and name the resultant molecular orbitals for

bonding and antibonding complete with notation.
• 2px and 2px
• 2py and 2py

2) Explain which species has the longest bond between

• N2 and N2+ • 2py and 2py
• O2 and O2+

3) Draw completely labeled molecular orbital for CN-.

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2) Explain which species has the 3) Draw completely labeled

longest bond between molecular orbital for CN.
6C 1s2 2s2 2p2
• N2 and N2+ 7N 1s2 2s2 2p3

N2 1/2(8 − 2) = 3

N2+ 1/2(7 − 2) = 2.5

• O2 and O2+
O2 1/2(8 − 4) = 2
Energy

O2+ 1/2(8 − 3) = 2.5

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