Advanced Theories of Covalent Bonding

• Valence Bond Theory

• Hybridization of Atomic Orbitals
• Multiple Bonds
• Molecular Orbital Model
 Valence Shell Electron Pair Repulsion
(VSEPR) Theory
• In molecules or polyatomic ions valence electrons
exist in pairs;
• Electron pairs repel each other:
they are arranged in an orientation that gives
minimum electron-pair repulsions;
• Relative strength of electron-pair repulsions:
Nonbonding pair repulsion > Nonbonding-bonding
repulsion > bonding pair repulsion;
 Determination of Molecular Shapes by the
VSEPR Model
• Molecular shapes determined by number and
orientation of electron-pairs around central
atom;
• Shapes with minimum electron-pairs repulsion
are preferred:
Nonbonding pairs placed farthest apart from
each other.
• Summary of Molecular Shapes predicted using the VSEPR Model
• ———————————————————————————————————————
• # of E-pair # of # of Molecular
• e-pairs Geometry bond-pairs Lone-pairs Shapes Examples
• ———————————————————————————————————————
• 2 Linear 2 0 Linear BeCl2
• 3 trigonal 3 0 Trigonal BF3
• planar planar
• 3 '' 2 1 V-shape GeCl2
• 4 tetrahedral 4 0 Tetrahedral CCl4
• 4 '' 3 1 Trigonal
• pyramidal PCl3
• 4 '' 2 2 V-shape SCl2
• 5 trigonal 5 0 Trigonal
• bipyramidal bipyramidal AsCl5
• 5 '' 4 1 See-saw SeCl4
• 5 '' 3 2 T-shape ClF3
• 5 '' 2 3 Linear KrF2
• 6 octahedral 6 0 Octahedral SeCl6
• 6 '' 5 1 Square-
• pyramidal ICl5
• 6 '' 4 2 Square
• planar XeF4
• ——————————————————————————————————————
Molecular Shapes by VSEPR Model
 How to Predict Polarity

• Polarity of molecule depends on molecular

shape and bond polarity.
1. Molecules (or polyatomic ions) with symmetrical
shapes are non-polar;
2. Molecules with single lone-pairs on central
atoms are generally polar;
 Models for Chemical Bonding
• Localized electron model
(Valence bond method and orbital hybridization)
• Molecular orbital Theory
(Delocalized electron model)
 Localized Electron Model
• Good for explaining molecular shapes;
• Two singly occupied orbitals from separate atoms
form overlaps.
• Electron pairs occupy overlap area to form -bonds;
• Two types of covalent bonds may be formed:
1. -bond: orbitals overlap along internuclear axis
2.  -bond: side-to-side overlap of orbitals
perpendicular to the internuclear axis
 Orbital Hybridization

1. Hybridization describes the mixing of atomic

orbitals on the central atom to account for the
bond length, bond energy, and bond angle.
 H
Consider bonding in CH4
C
H
H
H

• Facts: Methane (CH4) has tetrahedral shape with bond

angles of 109.5o; all C-H bonds are identical.
1. If overlaps involve unhybridized orbitals, there would be
one 2s-1s overlap and three 2p-1s overlaps.
2. One C-H bond in CH4 would be different from the others.
3. Since 2p orbitals are perpendicular to one another, bond
angles in CH4 would be 90°.
Conclusion: overlap of orbitals in CH4 could not involve original
atomic orbitals on carbon.
1. Overlaps between pure atomic
orbitals lead to a molecular shape
that does not agree with that
predicted by VSEPR method or
with observed shape. That is,
a. One C─H bond (from 2s-1s
overlap) would be shorter;
b. Three C─H bonds (from 2p-1s
overlaps) would be longer and
at right angles to each other.
c. CH4 is tetrahedral and has
symmetrical shape

2. Elements involved in bonding will

modify their orbitals to achieve
minimum energy configuration.
 Hybridization of atomic orbitals in CH4
• The 2s and 2p atomic orbitals in carbon mix to form 4
identical hybrid orbitals for bonding. Mixing of
atomic orbitals is called hybridization.
• Hybridization of one 2s and three 2p orbitals yields
four sp3 hybrid orbitals on the carbon atom.
• Four sp3 hybrid orbitals around a central atom yield a
tetrahedral arrangement.
• Each sp3 hybrid orbital overlap with 1s orbital of H-
atom yields a tetrahedral molecule of CH4.
When a C-atom bonds to four other atoms, it hybridized its 2s
and 2p atomic orbitals to form 4 new sp3 hybrid orbitals

a. The shape of each sp3 orbital shape is a mixture of one 2s

and three 2p characters, yielding a large and a small
lobes
b. Number of hybrid orbitals same as number of atomic
orbitals hybridized.
All four sp3 orbitals have same energy level (degenerate)

H-atom can only use 1s orbital for bonding. The shared

electron pair can be found in the overlap area of H1s—Csp3
NH3 and H2O also use sp3 hybridization; lone pairs occupy some
of the hybrid orbitals.

H H
C C
H H
 Orbitals Hybridization

C. sp2 Hybridization
1. C2H4, ethylene is one example
2. Lewis and VSEPR structures tell us what to
expect
3. H atoms still can only use 1s orbitals
4. C atom hybridizes 2s and two 2p orbitals into 3
sp2 hybrid orbitals
Formation of C=C Double Bond in
Ethylene
5. The new sp2 orbitals are degenerate and in the same plane
6. One 2p orbital is unhybridized; it is perpendicular to the sp 2
plane

7. One C—C bond in ethylene formed by overlap of sp 2 orbitals,

one from each C atoms, is called sigma (s) bond - the overlap
is along the internuclear axis.
8. The second C—C bond formed by overlap of unhybridized 2p
orbitals, is called pi (p) bond because the overlap is
perpendicular to the internuclear axis. 
H H
C C
H H
– 9. Pictorial views of the orbitals in ethylene
The Sigma System for Benzene
Resonance in Benzene
 Delocalization
• Describes molecules that require resonance.
• In molecules that require resonance, it is the 
bonding that is most clearly delocalized, the  bonds
are localized.
• p orbitals perpendicular to the plane of the molecule
are used to form  molecular orbitals.
• The electrons in the  molecular orbitals are
delocalized above and below the plane of the
molecule.
The Pi System for Benzene
D. sp Hybridization
1. CO2, carbon dioxide is our example O C O
2. Lewis and VSEPR predict linear structure
3. C atom uses 2s and one 2p orbital to make two sp hybrid orbitals
that are 180 degrees apart

4. We get 2 degenerate sp orbitals and two unaltered 2p orbitals

5. Oxygen uses sp2 orbitals to overlap and form sigma bonds with C
6. Free p orbitals on the O and C atoms form pi bonds to complete
bonding
E. d-orbitals can also be involved in hybridization
1. dsp3 hybridization in PCl5

2. d2sp3 hybridization in SF6

 Types of Hybridization

• There are five different types of hybridization:

1. sp - required by two pairs of electrons around an atom.
2. sp2 - required by three pairs of electrons around an atom.
3. sp3 - required by four pairs of electrons around an atom.
4. dsp3 - required by five pairs of electrons around an atom.
5. d2sp3 - required by six pairs of electrons around an atom.
• A bond acts as one effective pair of electrons whether
it is a single, double, or triple bond.
 Hybridization and the Localized
Electron Model

# Electron-pairs on
Central Atom Arrangement Hybridization
2 linear sp
3 trigonal planar sp2
4 tetrahedral sp3
5 trigonal bipyramid dsp3 or sp3d

6 octahedral d2sp3 or sp3d2

F. The Localized Electron Model
1. Draw the Lewis
structure(s)

2. Determine the arrangement

of electron pairs (VSEPR
model).

3. Specify the necessary

hybrid orbitals.
 Exercise
Draw the Lewis structure for PCl5.
 What is the shape of a phosphorus
pentachloride molecule?
trigonal bipyramidal Cl Cl
 What are the bond angles? Cl P Cl
90 and 120
o o

Cl
 sp d or dsp Hybridization
3 3

• Hybridization of a 3s, three 3p, and a 3d orbitals

yields five sp3d hybrid orbitals.
• Five hybrid orbitals yield a trigonal bipyramidal
arrangement.
• If all five orbitals form covalent bonds, a molecule
with trigonal bipyramidal shape is obtained.
The Orbitals used to form the Bonds in PCl5
 Exercise
Draw the Lewis structure for XeF4.
 What is the shape of a xenon tetrafluoride
molecule?
octahedral
 What are the bond angles? F
90o and 180o F Xe F
F
 sp d or d sp Hybridization
3 2 2 3

• Combination of one s, three p, and two d

orbitals yields six sp3d2 hybrid orbitals;
• Six equivalent sp3d2 hybrid orbitals around a
central tom gives an octahedral arrangement.
• If all six orbitals form covalent bonds, an octahedral
molecule is obtained.
Hybridization of the Xenon Atom in XeF4
 Concept Check
Draw the Lewis structure for HCN.
Which hybrid orbitals are used?
Draw HCN:
 Showing all bonds between atoms.
 Labeling each bond as  or .
 Concept Check
Determine the bond angle and expected
hybridization of the central atom for each
of the following molecules:
NH3 SO2KrF2 CO2 ICl5
NH3 – 109.5o, sp3
SO2 – 120o, sp2
KrF2 – 90o, 120o, dsp3
CO2 – 180o, sp
ICl5 – 90o, 180o, d2sp3
 Using the Localized Electron Model

• Draw the Lewis structure(s).

• Determine the arrangement of electron
pairs using the VSEPR model.
• Specify the hybrid orbitals needed to
accommodate the electron pairs.
 Exercise #1 on Hybridization
Describe the bonding in the water molecule using the localized
electron model.

Solution

O
H H
• Since there are four electron pairs around oxygen atom, the
oxygen is sp3 hybridized. The water molecule has a bent
structure (or V-shape)
 Sigma () and Pi () Bonds

• Bonds formed by end-to-end overlaps of orbitals

along the orbital axes are called sigma (σ) bonds.
• Bonds formed by sidewise overlaps between two
parallel unhybridized p-orbitals are called pi (π)
bonds. The overlaps of orbitals occur above and
below the bond axis
• All single bonds are σ-bonds.
• A double bond consists of one σ bond and one π
bond.
• A triple bond is made up of one σ and two π bonds.
 Exercise #2 on Sigma and Pi Bonds

How many σ bonds are there in the commercial insecticide,

“Sevin,” shown below? How many π bonds?

Solution
There are 27 σ bonds.
There are 6 π bonds.
 Practice with Hybrid Orbitals
Give the hybridization and predict the geometry of the central
atom in the ion IF2+.

Lewis structure: F I F

There are 4 effective electron pairs around the central atom

making it sp3 hybridized.

The VSEPR structure has a tetrahedral basis but since it has two
bonding pairs, it will take on a bent shape with a bond angle
smaller than 109.5°.
 Molecular Shape of SOF4

1. SOF4

2. Sulfur in SOF4 has 5 electron pairs. The VSEPR

structure is a trigonal bipyramid. Sulfur is sp3d
hybridized.
O
F
F S
F
F
 Hybridization and Structure of C2H2

3. HC≡CH
Each carbon has 2 effective electron pairs.
The VSEPR structure is linear. Each carbon is
sp hybridized.

H C C H
 The Molecular Orbital Model

• The localized electron model does an excellent job in

predicting and justifying molecular shapes. But it
does not deal with molecules with unpaired electrons.
It also neglects bond energies.

• The molecular orbital (MO) model views electrons as

belonging to the entire molecule rather than to
individual atoms in the molecule.
• MO theory allows us to get a clearer understanding of
resonance.
 Molecular Orbital Theory

• Regards a molecule as a collection of nuclei

and electrons, where the electrons are assumed
to occupy orbitals that extend over the entire
molecule.
• Electrons fill molecular orbitals in the same
manner they do the atomic orbitals.
• The electrons are assumed to be delocalized
rather than always located between a given
pair of atoms.
 Electron Probability in MO

• The electron probability of both

molecular orbitals is centered along the
line passing through the two nuclei.
 Sigma (σ) molecular orbitals (MOs)
• In the molecule only the molecular
orbitals are available for occupation by
electrons.
 Key Ideas of the MO Model

1. All valence electrons in a molecule exist in a set of

molecular orbitals of a given energy.
2. Valence orbitals of each atom are not acting
independently, but rather interact as a whole to
form a set of molecular orbitals.
3. Each pair of atomic orbitals interacts to form a set
of bonding and antibonding molecular orbitals.
4. Energy for bonding molecular orbitals is lower than
their atomic orbitals.
5. Antibonding molecular orbitals have higher energy
that their atomic orbitals.
Combination of Hydrogen 1s Atomic
Orbitals to form MOs
 Figure 9.26: (a) MO Energy-Level
Diagram for H2 Molecule, (b) Shapes of MOs
MO Energy-Level Diagram for the H2
Molecule
 Bond Order in MO Model

# bonding electrons - # antibonding electrons

BO =
2

1. Bond order (BO) is a measure of net bonding

interactions.
2. BO must be greater than 0 for a stable molecule to
form.
3. The higher the BO, the stronger the bond.
Example: H2

2  0
Bond order = =1
2
 Bond Order inH2-

2  1 1
Bond order = =
2 2
 Bond Order

• Larger bond order means greater bond

strength.
# of bonding e   # of antibonding e 
Bond order =
2
MO Energy-Level Diagram for He2 Molecule
Figure 9.33: Three Mutually Perpendicular
2p Orbitals on Two Adjacent Boron Atoms
Constructive Interference from
Combining Parallel p Orbitals
Set of π MOs
Figure 9.34: Expected MO Energy-Level Diagram
from Combination of 2p Orbitals on Boron
Expected MO Energy-Level Diagram for
B2 Molecule
The Correct MO Energy-Level
Diagram for B2 Molecule
 MO Energy-level Diagram for B2

• Filling molecular orbitals 2s

and 2p works the same as σ*2p
when filling 1s orbitals.
π*2p
• Fill degenerate orbitals
2pseparately, then pair-up σ2p
with electrons having E
opposite spins. π2p
• Molecular orbital diagram
shows that B2 molecule is
σ*2s
paramagnetic.
• BO in B2 = ½ (4 – 2) = 1 σ2s
 MO Energy-level Diagram for C2

σ*2p
• Molecular orbital
diagram for C2 shows π*2p
that the molecule is σ2p
diamagnetic. E
• Bond order in C2 π2p
= ½ (6 – 2) = 2
σ*2s

σ2s
 MO energy-level diagram for N2

σ*2p
• Molecular orbital
diagram for N2 shows π*2p
that it is diamagnetic. σ2p
Bond order in N2 E
= ½ (8 – 2) = 3 π2p

σ*2s

σ2s
Molecular Orbital Summary of Second
Row Diatomic Molecules
 MO Energy-level Diagram for O2

σ*2p
• It shows that O2
molecules is π*2p
paramagnetic σ2p
• Bond order in O2 : E
½ (8 – 4) = 2 π2p

σ*2s

σ2s
 Paramagnetism

• Paramagnetism – substance is attracted

into the inducing magnetic field.
 Unpaired electrons (O2)
• Diamagnetism – substance is repelled
from the inducing magnetic field.
 Paired electrons (N2)
Apparatus Used to Measure the
Paramagnetism of a Sample
Fig 9.39: Liquid Oxygen Poured into Space
Between Poles of Magnet

Donald W. Clegg
 Paramagnetism vs. Diamagnetism

• Paramagnetism implies the presence of

unpaired electrons, whereas diamagnetism
implies that all electrons are paired.
• Atoms or molecules that have paramagnetic
property are attracted to a magnetic field.
• Atoms or molecules that are diamagnetic
indicates are repelled by magnetic field.
• Paramagnetic effect is generally much stronger
than diamagnetic effect.
Figure 9.40: MO Energy-Level
Diagram for NO Molecule
MO Energy-Level Diagram
for NO+ and CN- Ions
 Homonuclear Diatomic Molecules

• Composed of 2 identical atoms.

• Only the valence orbitals of the atoms
contribute significantly to the molecular
orbitals of a particular molecule.
 Heteronuclear Molecules

• Heteronuclear molecules are molecules made up of

different atoms.
• Molecules that are made up of atoms close together
on the periodic table have similar molecular orbital
diagrams as homonuclear molecules.
• When two atoms of a diatomic molecule are very
different, the energy-level diagram is more
complicated.
Heteronuclear Diatomic Molecule: HF

• The σ molecular orbital containing the bonding

electron pair shows greater electron probability close
to the fluorine.
• The electron pair is not shared equally.
• This causes the fluorine atom to have a slight excess
of negative charge and leaves the hydrogen atom
partially positive.
• This is exactly the bond polarity observed for HF.
 The Electron Probability Distribution in the
Bonding Molecular Orbital of the HF Molecule
Orbital Energy-Level Diagram for the
HF Molecule
Heteronuclear Diatomic Molecule: HF

• The 2p orbital of fluorine is at a lower energy

than the 1s orbital of hydrogen because fluorine
binds its valence electrons more tightly.
 Electrons prefer to be closer to the fluorine atom.
• Thus the 2p electron on a free fluorine atom is at
a lower energy than the 1s electron on a free
hydrogen atom.
 Bonding in Heteronuclear molecules
• The HF molecular orbital
diagram is given at right.

• Because the fluorine 2p

orbital is lower in energy
than the hydrogen 1s
orbital, the electrons
prefer to be closer to the
fluorine atom.
 Bonding in Homonuclear Diatomic Molecules

• Bonds are formed when atomic orbitals overlap in space.

• This is not possible with 1s orbitals in period two elements
because each of the orbitals is too close to its own nucleus.
• Only the 2s and 2p orbitals (containing the valence electrons)
can participate in bond formation.
• Sigma (σ) bonds are formed along internuclear axis. Sigma
type molecular orbitals can be formed using 2s orbitals or 2px
orbitals (assuming bonding along the x-axis)
• In addition, pi (π) type molecular orbitals are formed by the
combination of 2py or 2pz orbitals.
• The combination of atomic orbitals yields bonding (and )
and antibonding (σ* and π*) molecular orbitals.
 Exercise #2 on Molecular Orbitals
Determine the electron configuration and bond order for the
following. If it exists, discuss its magnetism.
1. F2-
σ*2p
How many valence electrons
does F2- have? π*2p
15 valence electrons
σ2p
E
8 b.e. - 7 a.e.
BO = 2
=½ π2p

σ*2s
F2- would be paramagnetic.
σ2s
 Exercise #3 on Molecular Orbitals
Determine the electron configuration and bond order for the
following. If it exists, discuss its magnetism.
2. S22-
σ*3p
How many valence electrons
does S22- have? π*3p
14 valence electrons
σ3p
8 b.e. - 6 a.e. E
BO = =1
2 π3p

S22- would be diamagnetic. σ*3s

σ3s
 Exercise #4 on Molecular Orbitals
Determine the electron configuration and bond order for the
following. If it exists, discuss its magnetism.
3. Cl22+
σ*3p
How many valence electrons
does Cl22+ have? π*3p
12 valence electrons
σ3p
E
8 b.e. - 4 a.e.
BO = =2 π3p
2

σ*3s
Cl22+ would be paramagnetic.
σ3s
 Combining the Localized Electron and
Molecular Orbital Models
• Advantage of molecular orbital model - correctly
predicts relative bond strength and magnetism of
simple diatomic molecules.

• It can account for bond polarity and correctly

portrays electrons as being localized or delocalized in
polyatomic molecules.

• Major disadvantage - too complex for polyatomic

molecules. An approximation is used.
 Combining the Localized Electron and
Molecular Orbital Models
• The localized electron model assumes that electrons are
confined between a given pair of atoms in a molecule.
• Combining the localized electron and molecular orbital
models gives us a more accurate description, such that:
σ-bonds can be regarded as localized, while
π-bonding is best described as delocalized.
• Since a double bond consists of one σ-bond and one π-bond:
Electrons in σ-bonds are considered localized.
Electrons involved in -bonds are said to be delocalized.
Delocalized pi bonding in benzene molecule
 Molecular Orbital Energies

• MO1 is lower in energy than the s orbitals

of free atoms, while MO2 is higher in
energy than the s orbitals.
 Bonding molecular orbital – lower in energy
 Antibonding molecular orbital – higher in
energy
 Electron Configurations in MO

• Molecular electron configurations can be

written similar to atomic electron
configurations.
• Each molecular orbital can hold 2 electrons
with opposite spins.
• The number of orbitals are conserved.
Bonding in H2
Sigma Bonding and Antibonding
Molecular Orbitals
 MO energy-level diagram for first period
elements
• To fill molecular orbitals
for atoms containing 1s
valence electrons σ*1s
(hydrogen and helium):
1. Determine the number of
electrons in the molecule.
2. Fill the energy level
diagram from lowest to E
highest energy.
3. Fill each orbital with a
pair of electrons and with σ1s
opposite spins.
 Exercises on Molecular Orbitals
Use MO theory to describe the bonding and stability of
a. H22- b. H2+
H22- has 4 electrons. H2+ has 1 electron.

σ*1s σ*1s

σ1s σ1s

2 b.e. - 2 a.e. 1 b.e. - 0 a.e.

BO = =0 BO = 2 =½
2

(H2+ may be formed, but it would not be much

H2 ion will not be formed.
2-
more stable than two separate hydrogen atoms)
Pi Bonding and Antibonding Orbitals