Chapter 8: Advanced Theories of Covalent

Bonding
 Learning Objectives

1. Describe the principles of valence bond theory (8.1

OpenStax)
2. Interpret an energy diagram for bond formation with
respect to internuclear distance (8.1 OpenStax)
 Valence Bond Theory
• Valence bond theory: electrons reside in quantum-
mechanical orbitals localized on individual atoms.
Chemical bonds result from an overlap of orbitals.
For a system of two atoms approaching each other
− if energy of the system is lowered  a chemical bond
forms.
− if energy of the system is raised  a chemical bond does
not form.
 Valence Bond Theory: Orbital Interaction
• Chemical bonds result from an overlap of standard
and/or hybridized atomic orbitals with negative interaction
energy (more stable) than the separated atomic orbitals.

• A chemical bond results from the overlap of:

1. Two half-filled orbitals with spin-pairing of the two

valence electrons, or

2. One completely filled orbital with an empty orbital (less

commonly)

• The geometry of the overlapping orbitals determines the

shape of the molecule
 Learning Objectives

3. For any Lewis structure, predict hybridization, orbital

overlap, and number of sigma and pi bonds. (8.1 – 8.3
OpenStax)
4. Describe the orbitals that contribute to each
hybridization scheme (8.2)
5. Describe the relationship between hybridization and
bond type (8.3)
Sigma (σ) bonds form from the overlap of : (a) two s orbitals,
(b) an s orbital and a p orbital, and (c) two p orbitals. The
dots indicate the locations of the nuclei.

(a) (b) (c)

Pi ( ) bonds form from the side-

by-side overlap of two p orbitals.
The dots indicate the location of
the nuclei.
 Sigma (σ) and Pi (𝛑) Bonds

• While all single bonds are σ bonds, multiple bonds

consist of both σ and π bonds.

 bond
 Practice 1:
C4H6, is used to make synthetic rubber. Identify the
number of σ and π bonds contained in this molecule.

A) 2 σ and 9 π bonds
B) 2 σ and 7 π bonds
C) 6 σ and 2 π bonds
D) 7 σ and 2 π bonds
E) 9 σ and 2 π bonds
 Practice 2:

Identify each illustration as depicting a σ or π bond:

(a) side-by-side overlap of a 4p and a 2p orbital π
(b) end-to-end overlap of a 4p and 4p orbital σ
(c) end-to-end overlap of a 4p and a 2p orbital σ
 Bond Rotation
Rotation about a single bond (σ bond) is allowed.
− Rotation around a σ bond does not break the interaction
between the orbitals.

Rotation about a double bond (one π bond and one σ bond)

is severely restricted.
– Rotation around a π bond breaks the bond: a π bond
forms by interacting above and below (side-by-side) the
internuclear axis
 Practice 3:

According to VB theory, sigma bonds are:

A) Formed from side by side overlap (also called side-
on overlap) of orbitals
B) Always present in double bonds
C) Formed only by the overlap of two unhybridized
orbitals
D) Formed only by the overlap of p orbitals
E) Formed only by the overlap of s orbitals
 Practice 4:

Draw the Lewis structure for the molecule CH2CHCH3.

How many sigma and pi bonds does it contain?

A. 8 σ, 1 π
B. 9 σ, 0 π
C. 9 σ, 1 π
D. 7 σ, 2 π
E. 8 σ, 2 π
 Summary: Bond Types

Bond Type # of σ-bonds # of π-bonds

Single 1 0
Double 1 1
Triple 1 2
 Orbital Diagram for the Formation of H2O
H ↿ Half-filled
orbitals
Focus on valence
orbitals only
1s
overlap

H ↿ H−O bonds
1s

↿↿

⇌
⇌

⇌
⇌
⇌
⇌

O H2O
2s 2s 2s 2s

Valence bond theory:

Predicted bond angle = 90°
VSEPR: H O H bent
Predicted bond angle <109.5º
Actual bond angle = 104.5°
 ”Regular” Orbitals Aren’t the Whole Story
Issues with assuming the overlapping orbitals that form
chemical bonds are standard s, p, or d atomic orbitals:
Sometimes, predicted number of bonds or orientation of
bonds are wrong.

Example:
H
H
109.5o
1s H
C
H
H
C
Predicted Observed
2s 2p
Two bonds Four bonds
90º bond angle 109.5º bond angle
 Hybridization Ideas:
• Hybrid orbitals don’t exist in isolated atoms. Only formed in
covalently bonded atoms.
• Hybrid orbitals have shapes and orientations that are different
from those of the atomic orbitals in isolated atoms.
• A set of hybrid orbitals is generated by combining atomic
orbitals. The # of hybrid orbitals = # of atomic orbitals that were
combined to produce the set.
• All orbitals in a set of hybrid orbitals are equivalent in shape and
energy (degenerate).
• The type of hybrid orbitals formed in a bonded atom depends
on its electron-pair geometry as predicted by the VSEPR theory.
• Hybrid orbitals overlap to form σ bonds. Unhybridized orbitals
overlap to form π bonds.
 sp Hybridization
    
p Unhybridized
E   p orbitals


Hybrid sp
s
orbitals
Standard
atomic orbitals
Orbitals Combined
One s and one p

Orbitals Produced
Two sp hybrid orbitals

Hybrid Orbital Appearance Linear

Geometry
Two sp hybrid orbitals
 sp2 Hybridization
   
p Unhybridized
E    p orbital

 Hybrid sp2
s orbitals
Standard
atomic orbitals
Orbitals Combined
One s and two p orbitals

Orbitals Produced
Three sp2 hybrid orbitals

Hybrid Orbital Appearance Trigonal

Planar
Three sp2 hybrid orbitals Geometry
 sp3 Hybridization
  
p    
E
Hybrid sp3
 orbitals
s
Orbitals Combined
Standard
atomic orbitals One s and three p orbitals

Orbitals Produced
Four sp3 hybrid orbitals

Hybrid Orbital Appearance

Four sp3 hybrid orbitals
Tetrahedral
109.5°
Geometry
 Hybridization
Number of
Hybridization Number of Number of Number of
hybrid
Scheme s orbitals p orbitals d orbitals
orbitals
sp3 1 3 0 4

sp2 1 2 0 3

sp 1 1 0 2

sp3d 1 3 1 5

sp3d2 1 3 2 6

Expanded octets
• The number of standard atomic orbitals combined = the
number of hybrid orbitals formed.
• Central atoms have the greatest tendency to hybridize.
• Hybridization yields the lowest energy for the molecule.
 Practice 5:

Some very rare compounds exhibit 7-coordinate geometry.

What would be the hybridization scheme for these?
A. sp3
B. sp3d
C. sp3d2
D. sp3d3
E. sp3d4
 Practice 6:
According to valence bond theory, which orbitals are
present for the carbon atom of formaldehyde (CH2O)?

A) Three sp2 orbitals

B) Three sp2 orbitals and an unhybridized p orbital
C) Three sp3 orbitals and an unhybridized p orbital
D) Two sp2 orbitals and one sp orbital
E) Three sp3 orbitals
 Practice 7:
Consider the molecule below. Determine the hybridization
at each of the 3 labeled atoms that refer, in order, to a
carbon, another carbon and an oxygen.

A.1=sp2, 2=sp3, 3=sp2

B.1=sp2, 2=sp3, 3=sp3
C.1=sp3, 2=sp3, 3=sp3
D.1=sp3, 2=sp3, 3=sp2
E.1=sp, 2=sp2, 3=sp2
 Practice 8:
1 2

O 3

H N C C O H

Which bond(s) do not allow free rotation?

A. Only 1
B. Only 2
C. Only 3
D. Both 1 and 2
E. All three
 Practice 9:
Which statement is correct for the structure shown?

A) Carbon number 7 is described by sp hybridization.

B) The molecule contains 19 σ bonds.
C) The molecule contains a total of five π bonds.
D) Carbon number 1 is described by sp3 hybridization.
E) Carbon number 2 is described by sp2 hybridization.
 Learning Objectives

6. Define bonding and antibonding orbitals. (8.4 OpenStax)

 Molecular Orbital (MO) Theory

Valence bond theory presumes the electrons are localized in

individual orbitals on the atoms in the molecule − it doesn’t
account for delocalization.

In molecular orbital theory, Schrödinger’s equation is applied

to the entire molecule to obtain a set of molecular
orbitals.

The electrons belong to the whole molecule

(delocalization)
 Linear Combination of Atomic Orbitals
The bonding molecular orbital arises out of constructive
interference between the overlapping atomic orbitals
(same phase).
The antibonding molecular orbital arises out of
destructive interference between the overlapping atomic
orbitals (opposite phases).
p orbitals can produce
sigma and/or pi overlap,
depending on how the
two atoms forming the
molecular bond interact.
 Learning Objectives

7. Use molecular orbital theory to determine the bond

order for diatomic molecules given the MO diagram.
(8.4 OpenStax)
 Molecular Orbital Energy Diagram for Be 2+
• Step 1: Fill atomic orbitals on
both sides
• Step 2: Copy the electrons
from the atoms into the
center boxes by filling the
lowest energy MOs first with
a maximum two electrons
per box
• Step 3: For molecular
orbitals at the same energy
level, follow Hund’s rule by
filling the orbitals singly first
 Molecular Orbital Energy Diagrams for C 2
C C
*2p

*2p

2p

C: 1s22s22p2 2p

*2s

2s
 MO Energy Diagrams for for Second-Period
Diatomic Molecules
Atomic Molecular Atomic Atomic Molecular Atomic
orbitals orbitals orbitals orbitals orbitals orbitals

*2p *2p

*2p *2p

2p 2p 2p
2p
2p 2p

2p 2p

B2, C2, N2 Energy O2, F2, Ne2

*2s *2s

2s 2s 2s 2s

2s 2s
 Bond Order – from Number of Bonds
• Bond order is the number of chemical bonds between
a pair of atoms.
– Bond order is 1 for a single bond
– Bond order is 2 for a double bond
– Bond order is 3 for a triple bond

Example:
• Diatomic nitrogen N≡N: the bond order is 3
• Acetylene H−C≡C−H:
– the bond order between the two carbon atoms is 3
(triple bond)
– the C−H bond order is 1 (single bond)
 Bond Order – from MO Diagrams
( ¿ 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑀𝑂𝑠 ) − ( ¿ 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝑎𝑛𝑡𝑖𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑀𝑂𝑠 )
𝐵𝑜𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 =
2

Example: Bond order of H2 =

Bond order of He2 =

Bond order:
– Positive: A chemical bond will form
– Negative or zero: A chemical bond will not form
– May be a fraction (Bond order of He2+ ions is ½)
– Higher bond order = stronger bonds
 Molecular Orbital Energy Diagrams for C 2
C C
*2p

*2p

2p

C: 1s22s22p2 2p

*2s

What is the bond order?

(focus on the center only)
2s
 Practice 10:
Which of the following statements
is true regarding Ne22+?
A) Its bonding order is 0 and it is
not expected to exist.
B) Its bonding order is 1 and it is
not expected to exist.
C) Its bond order is 0 and it is
expected to exist.
D) Its bond order is 1 and it is
expected to exist.
E) Its bond order is 3/2 and it is
expected to exist.
Bond order = (8-6)/2 = +1
 MO Energy Diagrams for for Second-Period
Homonuclear Diatomic Molecules
Large 2s-2p interaction Small 2s-2p
interaction
B2 C2 N2 O2 F2 Ne2

⇌ ⇌ ⇌ ⇌ ⇌
⇌ ⇌ ⇌ ⇌
⇌ ⇌

⇌ ⇌
⇀
⇀
⇌ ⇌ ⇌
⇌
⇌ ⇌
⇌ ⇌
⇌

⇌ ⇌
⇀
⇀
⇌

⇌
⇌
⇌

⇌
Bond order 1 2 3 2 1 0
Bond energy (kJ/mol) 290 620 946 498 159 –
Bond length (pm) 159 131 110 121 143 –
 Learning Objectives

8. Use molecular orbital theory to make predictions for

diamagnetism and paramagnetism. (8.4 OpenStax)
 O2 O2

• A substance is paramagnetic if its MO

⇀
⇀
diagram has unpaired electrons.

⇌ ⇌ ⇌
⇌
• If all electrons are paired, it is diamagnetic.
• Dioxygen is paramagnetic.

Magnet

⇌
↿↿ ↿↿
↿ ↿ ↿ ↿
↿↿ ↿↿ ↿↿↿ ↿↿↿↿
↿ ↿ ↿ ↿↿ ↿ ↿
↿ ↿↿ ↿↿↿↿↿↿ ↿↿↿ ↿
↿ ↿ ↿↿ ↿
↿ ↿↿ ↿↿ ↿
↿ ↿↿
A Gouy balance compares the mass of a sample in the
presence of a magnetic field with the mass with the
electromagnet turned off to determine the number of
unpaired electrons in a sample.
 Take-Home Message
• You’re not expected to memorize the MO diagrams for
each molecule
• Be able to:
– Complete a MO diagram for a molecule given a blank
energy diagram
– Solve for the bond order of a molecule
– Determine para or diamagnetic