CHEMISTRY

Chapter 8
Advanced Theories of
Covalent Bonding
CHAPTER 8: ADVANCED THEORIES
OF COVALENT BONDING

8.1 Valence Bond Theory

8.2 Hybrid Atomic Orbitals
8.3 Multiple Bonds
8.4 Molecular Orbital Theory

2
BONDING THEORIES
Lewis Theory and VSEPR
• Dots arrayed about a central atom represent bonds and lone pairs of
electrons.
• The arrangement of atoms in three-dimensions and molecular
geometry can be predicted.
• Molecular polarity can also be predicted from the molecular structure.

Valence Bond Theory

• Electrons are in orbitals on each atom.
• Orbitals may be hybrids and overlapping orbitals in space form bonds.

Molecular Orbital Theory

• Electrons are in orbitals spread over the entire molecule rather than
attached to specific atoms.
• This model accommodates experimental observations of magnetism
not compatible with other, simpler theories.
3
8.1 VALENCE BOND THEORY
VSEPR Theory Weaknesses
• VSEPR is model that can be used to predict three-dimensional
shapes of molecules.
• Bond angles seen in VSEPR models such as 109° and 120° do
not agree with the geometries of s, p, and d atomic orbital.

4
8.1 VALENCE BOND THEORY
Valence Bond Theory
• The covalent overlap of atomic orbitals, each containing a single
electron, that yields an electron pair and a bond between two
atoms is best described by valence bond theory.
• In valence bond theory, orbitals overlap when a portion of one
atomic orbital and a portion of a second atomic orbital occupy
the same region of space.

overlap of two s-orbitals overlap of two p-orbitals

to form a single bond to form a single bond
s-orbital and p-orbital overlap to
form a single bond 5
8.1 VALENCE BOND THEORY
Energy and Orbital Overlap
• The energy of a system depends upon orbital overlap.
• No overlap occurs when atoms are far apart and the energy is zero.
• As orbitals approach and
begin to overlap, each
electron begins to feel the
attraction of the nucleus in
the other atom.
• Electrons also begin to repel
each other, as do the nuclei.
• While separated, attractive
forces are greater than
repulsive forces, and the
energy of the system
decreases; a bond begins to
form.
6
8.1 VALENCE BOND THEORY
Energy and Orbital Overlap (continued)
• While moving together, overlap increases, and both attractions and
repulsions increase.
• At some specific distance between the atoms the energy reaches its
lowest value.
• This optimum distance between is where a stable bond between the
two atoms form.

What is happening on
the left side of the plot?
7
8.1 VALENCE BOND THEORY
Bond Energy and Bond Length
• The bond energy is the ∆E between the energy minimum (at the
bond length) and the two separated atoms.
• This is the energy required to separate the atoms completely
and break the bond.
• This is therefore also the energy released when the bond is
formed.

7.24 x 10-19 J required to

break one H-H bond.

What is the energy

required to break one mole
of H-H bonds?

8
8.1 VALENCE BOND THEORY
Orbital Overlap: Distance and Orientation
• The formation of a bond depends upon the distance between
atomic nuclei and the orientation of the orbitals involved.
• Orbitals overlap most effectively when they are oriented on a
direct line between two nuclei.
• The overlap between two s-orbitals is simple because they are
spherically symmetric.

• When two p-orbitals interact to form a bond, orientation is

important so that overlap is maximized.

9
8.1 VALENCE BOND THEORY
Sigma (σ) and Pi (π) Bonds
• Sigma (σ) bonds are produced when overlap occurs between:
• two s-orbitals
• one s-orbital and one p-orbital
• two p-orbitals

• Pi (π) bonds are produced when two p-orbitals overlap in a

side-by-side orientation.

10
8.1 VALENCE BOND THEORY
Sigma (σ) and Pi (π) Bonds
• Single bonds are always σ–bonds.
• Multiple bonds are a combination of σ–bonds and π–bonds.
• double bond: one σ-bond, one π-bond
• triple bond: one σ-bond, two π-bond
• Molecules containing these types of bonds are shown below and
the bonds will be described in more detail later in the chapter.

11
8.1 VALENCE BOND THEORY
Example 8.1
Butadiene, C6H6, is used to make synthetic rubber. Identify the
number of σ and π bonds contained in this molecule.

Example 8.1 – Check Your Learning

Identify the type of bond depicted in each illustration.
8.2 HYBRID ATOMIC ORBITALS
Describing Orbital Overlap for Water
• A water molecule is a central oxygen atom bound to two
hydrogen atoms.
• The electron configuration for oxygen is 1s2 2s2 2p4
• It would make sense to predict that each of the ½ filled p-orbitals
would overlap with a spherical s-orbital from a hydrogen atom.

s-orbital from H

oxygen atom
s-orbital from H
(isolated) 13
8.2 HYBRID ATOMIC ORBITALS
Describing Orbital Overlap for Water
• The problem is that this model gives a molecular structure that is
does not match experimental evidence.
• The simple orbital overlap results in a molecule with a 90° bond
angle whereas experimental evidence shows that the bond
angle for water is 104.9°.

14
8.2 HYBRID ATOMIC ORBITALS
Describing Orbital Overlap for Water
• Returning to VSEPR theory, there are four regions of electron
density around an oxygen atom.
• This means that water is in the tetrahedral group.
• Water has two lone pairs of electrons and therefore has bent
molecular geometry.

• The bond angles observed experimentally show that valence

bond theory must include a hybridization component in order to
be an accurate model for bonding.

15
8.2 HYBRID ATOMIC ORBITALS
Hybrid Orbitals …
• do not exist in an isolated atom.
• only form when atoms come together to bond.
• have shapes/orientations very different from atomic orbitals.
• are generated by combining a set of atomic orbitals;
• # of hybrid orbitals created = # of atomic orbitals used.
• in a set are equivalent in shape and energy.
• depend upon electron-pair geometry and VSEPR theory.
• overlap to form σ–bonds; unhybridized orbitals must be used to
form π–bonds.

16
8.2 HYBRID ATOMIC ORBITALS
sp Hybridization
• One valence s-orbital mixes with a valence p-orbital to yield two
equivalent sp hybrid orbitals.

17
8.2 HYBRID ATOMIC ORBITALS
sp Hybridization
• One valence s-orbital mixes with a valence p-orbital to yield two
equivalent sp hybrid orbitals.

These hybrid sp orbitals

on Be overlap with Cl
atomic orbitals.
18
8.2 HYBRID ATOMIC ORBITALS
sp2 Hybridization
• Any central atom surrounded by three regions of electron
density forms a set of three sp2 hybrid orbitals.

Note the trigonal

planar arrangement.
120° 19
8.2 HYBRID ATOMIC ORBITALS
sp2 Hybridization
• Any central atom surrounded by three regions of electron
density forms a set of three sp2 hybrid orbitals.

These hybrid sp2

orbitals on B overlap
with H atomic orbitals. 20
8.2 HYBRID ATOMIC ORBITALS
sp3 Hybridization
• Any central atom
surrounded by
four regions of
electron density
forms a set of
four sp3 hybrid
orbitals.

Note the tetrahedral

arrangement.

21
8.2 HYBRID ATOMIC ORBITALS
sp3 Hybridization
• Any central atom surrounded by four regions of electron density
forms a set of four sp3 hybrid orbitals.

These hybrid sp3

orbitals on C overlap
with H atomic orbitals.

22
8.2 HYBRID ATOMIC ORBITALS
sp3 Hybridization
• The structure of ethane, C2H6, is similar to that of methane.
• Each carbon sits at the center of a tetrahedron, and each carbon
is sp3 hybridized.
• Rotation around the σ–bond bond created between the two
carbon atoms occurs readily.

23
8.2 HYBRID ATOMIC ORBITALS
sp3d and sp3d2 Hybridization
• To describe the five bonding orbitals in a trigonal bipyramidal
arrangement, five valence shell atomic orbitals must be used.
• one s + three p + one d = five sp3d hybrid orbitals
• For an octahedral arrangement with six bonding orbitals:
• one s + three p + two d = six sp3d2 hybrid orbitals
• These hybrid orbitals are only available for atoms having d-orbitals
in the third period and beyond.

trigonal bipyramidal octahedral

24
8.2 HYBRID ATOMIC ORBITALS
Summary of Hybridized Orbitals and Geometries

What is the hybridization

for SO42-?

What is the hybridization

for SF4?

What is the hybridization

for XeF4?

25
8.2 HYBRID ATOMIC ORBITALS
Examples
Identify the hybridization of indicated atoms.

iodine
sulfur

oxygen

sulfur

nitrogen

26
8.2 HYBRID ATOMIC ORBITALS
Examples
Three different analgesics are shown below. Identify the hybridization
of the indicated atoms.
H3 C HO H H H
H
C O C O
H C N C
O C C C C C H

H C C H C C O
aspirin C H
C C HO

H H H acetaminophen/
H paracetamol
H CH3
(Tylenol)
H
HO C C
C C C CH3

O C C CH
C C CH3
H
ibuprofen H H
H
(Motrin)
27
8.3 MULTIPLE BONDS
Sigma (σ) and Pi (π) Bonds in Molecules
• In ethene, C2H4, each carbon atom is surrounded by two
hydrogen atoms and another carbon atom.
• The three regions of electron density around each carbon
require sp2 hybrid orbitals.
• These hybrid orbitals combine to create one σ–bond and one
π–bond between the carbon atoms.
• There are also σ–bonds from each carbon atom to two hydrogen
atoms.

Ethene contains a total of 5 σ–bonds and 1 π–bond.

28
8.3 MULTIPLE BONDS
Sigma (σ) and Pi (π) Bonds in Molecules
• In acetylene, C2H2, each carbon atom is surrounded by one
hydrogen atom and another carbon atom.
• The two regions of electron density around each carbon require
sp hybrid orbitals.
• These hybrid orbitals combine to create one σ–bond and two π–
bond between the carbon atoms.
• There are also σ–bonds from each carbon atom to one
hydrogen atoms.

Acetylene contains a total of 3 σ–bonds and 2 π–bonds. 29

8.3 MULTIPLE BONDS
Examples
Determine the number of σ–bonds and π–bonds in each of the
analgesics shown below.
H3 C HO

C O C O

O C C

H C C H

C C
CH3 H acetaminophen/
H
aspirin H
H paracetamol
HO C C
(Tylenol)
σ–bonds: _____ C C C CH3

π–bonds: _____ σ–bonds: _____

O C C CH
C C CH3
π–bonds: _____
H
ibuprofen H
H
H
(Motrin)
σ–bonds: _____
π–bonds: _____ 30
Practice
What is the geometry and polarity for each molecule?

Molecule Lewis Structure Geometry Hybridization Polar?

a. BeF2

b. BF3

c. CF4

d. PF5

e. SF6
Practice
What is the geometry and polarity for each molecule?

Molecule Lewis Structure Geometry Hybridization Polar?

f. NH3

g. SF4

h. ClF3

i. XeF2

j. ICl4-
Practice
What is the geometry and polarity for each molecule?

Molecule Lewis Structure Geometry Hybridization Polar?

k. H2O

l. ClF2+

m. BrF5

n. XeF4

o. XeOF4
8.4 MOLECULAR ORBITALS

• Start by considering the Lewis Structure of O2

• All the electrons are paired.
• Yet, oxygen is attracted to a magnetic field, which
only occurs with unpaired electrons. Why do we see
it with oxygen?

34
8.4 MOLECULAR ORBITALS

Key Terms

• Paramagnetic: attracted to a magnetic field

• Diamagnetic: not attracted (weakly repel) a

magnetic field

• Neither act as permanent magnets, but demonstrate

attraction and repulsion in an applied magnetic field

35
8.4 MOLECULAR ORBITALS

MO Theory helps explain these observation by using a

combination of atomic orbitals to yield molecular
orbitals that are delocalized over an entire molecule
rather than being localized on atoms!

Explains…
• Paramagnetism of molecules like O2
• Resonance

36
8.4 MOLECULAR ORBITALS
Comparison of Bonding Theories
• Valence Bond Theory:
1. Considers bonds localized between one pair of atoms
2. Creates bonds from overlap of atomic orbitals (s, p, d…) and
hybrid orbitals (sp, sp2, sp3…)
3. Forms σ or π bonds
4. Predicts molecular shape based on the number of regions of
electron density
5. Needs multiple structures to describe resonance
• MO Theory:
1. Considers electrons delocalized throughout the entire molecule
2. Combines atomic orbitals to form molecular orbitals (σ, σ*, π, π*)
3. Creates bonding and antibonding interactions based on which
orbitals are filled
4. Predicts the arrangement of electrons in molecules
5. Explains resonance 37
8.4 MOLECULAR ORBITALS
MO Theory:
• Using quantum mechanics, the behavior of an electron in a
molecule is still described by a wave function, ψ (just like in an
atom)
• Electrons around atoms in molecules are limited to discrete
(quantized) energies.
• The region of space in which a valence electron in a molecule is
likely to be found is called a molecular orbital (ψ2).
• Like an atomic orbital, a molecular orbital is full when it contains
two electrons with opposite spins.

38
8.4 MOLECULAR ORBITALS
MO Theory:
• The mathematical process of combining atomic orbitals to
generate molecular orbitals is called the linear combination of
atomic orbitals (LCAO).
• We will consider homonuclear diatomic molecules (composed
of two identical atoms).

39
 Figure 8.28

(a) When in-phase waves combine, constructive interference produces a wave with
greater amplitude. (b) When out-of-phase waves combine, destructive interference
produces a wave with less (or no) amplitude.
8.4 MOLECULAR ORBITALS
MO Theory:
• The overlap of two molecular orbitals:
• σs: electron density between the nuclei
• This is a bonding orbital: electrons are attracted by both nuclei
at the same time and are more stable
• σs*: node between the nuclei
• This is an antibonding orbital: electrons are located away and
the nuclei are pulled apart

• Electrons fill the lower energy bonding orbital before they fill
higher energy antibonding orbitals

41
FIGURE 8.29

Sigma (σ) and sigma-star (σ*) molecular orbitals are formed by the combination of
two s atomic orbitals. The dots (•) indicate the locations of nuclei.

42
8.4 MOLECULAR ORBITALS
MO Theory:
• The wave function of p orbitals gives rise to two lobes with
opposite phases, shown by shading the lobes different colors.
• When orbitals of the same phase overlap, constructive wave
interference increases electron density.
• Destructive interference decreases electron density and creates
nodes.
• A similar process can occur with a p orbital to produce σ
bonding and a σ* antibonding orbital.

43
FIGURE 8.30

Combining wave functions of two p atomic orbitals along the internuclear axis creates
two molecular orbitals, σp and σ*p .

44
8.4 MOLECULAR ORBITALS
MO Theory:
• The remaining two sets of p orbitals are degenerate and
oriented side by side; thus, they combine to form two π orbitals
and two π* orbitals.
• Between two atoms, a total of six molecular orbitals result from
the combination of six atomic p orbitals.

45
FIGURE 8.31

Side-by-side overlap of each two p orbitals results in the formation of two π molecular
orbitals. Combining the out-of-phase orbitals results in an antibonding molecular orbital
with two nodes. One contains the axis, and one contains the perpendicular. Combining the
in-phase orbitals results in a bonding orbital. There is a node (blue line) directly along the
internuclear axis, but the orbital is located between the nuclei (red dots) above and below
this node.

46
8.4 MOLECULAR ORBITALS
MO Energy Diagrams:
• Energy levels of atomic and molecular orbitals are shown in a
molecular orbital diagram.
• Atomic orbitals of one atom are shown on the left and the other
on the right.
• Molecular orbitals formed from the combination are shown in the
center.
• Each line indicates an orbital that can hold two electrons.
• For each pair of atomic orbitals that combine, one bonding
and one antibonding MO results.
• Aufbau principle applies!
• Common to only show valence electrons

47
8.4 MOLECULAR ORBITALS

σ* σ*
π* π* π* π*
2p 2p 2p 2p
π π π π
σ σ

σ* σ*
2s 2s 2s 2s
σ σ
σ* σ*
1s 1s 1s 1s
σ σ
N N O O
N2 O2
8.4 MOLECULAR ORBITALS

diamagnetic paramagnetic

σ* σ*
↿ ↿
π* π* π* π*
2p ⥮ ⥮ 2p 2p ⥮ ⥮ 2p
π π π π
⥮ ⥮
σ σ
⥮ ⥮
σ* σ*
2s 2s 2s ⥮ 2s
⥮
σ σ
⥮ ⥮
σ* σ*
1s 1s 1s 1s
⥮ ⥮
σ σ
N N O O
N2 O2
8.4 MOLECULAR ORBITALS
Bond order:
• A filled MO diagram shows the number of electrons in both
bonding and antibonding MOs
• The net contribution of the electrons to the bond strength of a
molecule is determined by the bond order:

• Higher bond order = stronger bond

• Calculate the bond order of N2 and O2 based on their MO
50
8.4 MOLECULAR ORBITALS

Bond order = (10-4)/2 = 3, triple bond Bond order = (10-6)/2 = 2, double bond

σ* σ*
↿ ↿
π* π* π* π*
2p ⥮ ⥮ 2p 2p ⥮ ⥮ 2p
π π π π
⥮ ⥮
σ σ
⥮ ⥮
σ* σ*
2s ⥮ 2s 2s 2s
⥮
σ σ
⥮ ⥮
σ* σ*
1s 1s 1s 1s
⥮ ⥮
σ σ
N N O O
N2 O2