Summary of Last lecture

Covalent bond properties

– Bond length
– Bond strength
– Bond polarity

• Molecular polarity
 Chapter 5. Molecular Geometry and
Bonding Theories
Outline
1. Valence Shell Electron Pair Repulsion (VSEPR) Theory
2. Valence Bond Theory
3. Molecular Orbital Theory

Reference
1. “Chemistry, an atoms first approach”, S. S. Zumdahl, S. A.
Zumdahl, International Ed.; 2012, Chapters 4 and 5.

2
 1. Valence Shell Electron Pair
Repulsion (VSEPR) theory
• The shape of a molecule
plays an important role in
its reactivity.

• What determines the

shape of a molecule?

• A simple model based on

the number of bonding
and non-bonding electron
pairs will be described
here.
3
 1. Valence Shell Electron Pair Repulsion
(VSEPR) Theory
The Theory: the most stable arrangement of groups attached to
a central atom is the one that has the maximum separation of
electron pairs (bonded or non-bonded) to minimize electron pair
repulsions.

The Assumptions:
a) Each valence electron pair (bothbonding and non-bonding [lone
pair]) is important. A multiple bond is treated as a single electron pair.

b)Minimization of the repulsion of the electron pairs determines the

shape of molecules.
..
: F :
.. .. ..
6 pairs
S C N: : ..
.. : ..F I ..F :
:
2 pairs : ..
F
4
No. of e- pairs and geometry
No. of e- pairs idealized shape angele

2 E 180o
linear

3 E 120o

trigonal plane

4 E 109.5o

tetrahedron
5
No. of e- pairs and geometry
No. of e- pairs idealized shape angele

5 E 90o, 120o

trigonal bipyramid

6 E 90o,

octahedron

7 E 90o, 72o

pentagonal bipyramid 6
Examples

CX4 PCl5 SF6

7
 Modifications and Examples
• Spatial requirement for ..
H
lone pair (lp) is larger N
C H
than that of bonding H
H H H
electron pair (bp). H
o HNH = 107.3o
HCH = 109.5
• Thus the order of
repulsion of electron F
pair is following: F F F .. F
F ..
Xe Xe not Xe ..
F F F .. F F
lp/lp > lp/bp >bp/bp F

• The spatial O
requirement for a triple 120 o F
120 o o
126 126o
bond is larger than that C
of a double bond, B
F F F
which is larger than F o
that of a single bond. o
108
120
8
 Electronegativity Influence
S O
O O
H H Cl Cl
H H F F
o 92.2o o 111o
104.5 103.2

O S O O
H H H H F F Cl Cl
O is more electronegative, the bonding F is more electronegative, the bonding
electron pairs are more close to O. electron pairs are more close to F.

Question: Which one has a larger bond .. ..

angle? N P
F F
F F F F
9
 Electronegativity Influence
S O
O O
H H Cl Cl
H H F F
o 92.2o o 111o
104.5 103.2

O S O O
H H H H F F Cl Cl
O is more electronegative, the bonding F is more electronegative, the bonding
electron pairs are more close to O. electron pairs are more close to F.

Question: Which one has a larger bond .. ..

angle? N P
F F
F F F F
10
FNF = 102.1 o FPF = 93.3o
 General Procedure to Predict the
Shape of Molecules
a) Draw the Lewis structure.

b) Determine the geometry of the central atom based on

the number of electron pairs.

c) Distribute the lone pairs and surrounding atoms such

that the repulsion is minimized.

d) Only atoms are then considered for the shape.

11
 Examples
(b) O3
Molecular shape of (a) .. .. ..
Lewis structure: :O O O
HCN and (b) O3: .. ..

Parent structure: E
(a) HCN
Lewis structure: H C N : ..

Shape: .. O ..
Parent structure: E :O
.. O
..
Shape: H C N:
Bent or ..
Linear V-shape .. O ..
:O O
.. ..
12
* Only atoms are considered for shape
 Exercises
1. Predict the shape for NO2+.

NO2+

Lewis structure:

Parent structure:

Shape:

13
 Exercises
1. Predict the shape for NO2+.

.. .. +
Lewis structure: O N O
.. ..

Parent structure: E

.. .. +
Shape: O N O
.. ..

Linear

14
 Exercises
2. Predict the shape of (a) XeF2, (b) SF4 and (c)
SOF4.

15
 Exercises
2. Predict the shape of (a) XeF2, (b) SF4 and (c)
SOF4. (a) XeF2
Lewis structure: Parent structure:

.. .. .. ..
: F Xe F: E
.. .. ..

Possible shape:
..
F .. F ..
F
F Xe : Xe : Xe
.. F ..
.. .. F

lp/lp
16
lp/bp
 Exercises
2. Predict the shape of (a) XeF2, (b) SF4 and (c)
SOF4. (a) XeF2
Lewis structure: Parent structure:

.. .. .. ..
: F Xe F: E
.. .. ..

Possible shape:
..
Ignore F .. F ..
F Linear
interaction, : Xe
F Xe : Xe
if it is > 90o F ..
..
.. .. F Preferred

lp/lp 2 2 0
17
lp/bp 3 4 6
 Exercises
(b) SF4
Parent structure
.. .. ..
Lewis structure:: F S F:
..
..
E
F F

..
F ..
F
Possible Shape: F S F S
F F
F F
# lp/lp 0 0

# lp/bp 2 3

18
 Exercises
(b) SF4
Parent structure
.. .. ..
Lewis structure:: F S F:
..
..
E
F F

..
F ..
F
Possible Shape: F S F S
F F
F F
# lp/lp 0 0

# lp/bp 2 3
F
Shape of SF4:
Preferred F S
See-saw
F 19
F
 Exercises
3. For each pair below, select the one with a smaller angle.
(a) PH3 vs NH3, (b) BF3 vs PF3, (c) NH3 vs NH4+ (d) BF4- vs
XeF4

24
 Exercises
3. For each pair below, select the one with a smaller angle.
(a) PH3 vs NH3, (b) BF3 vs PF3, (c) NH3 vs NH4+ (d) BF4- vs
XeF4
.. .. ..
P F
N P
H H H B F
H H H F F F
F

F - F
.. H +
N B F Xe F
H N F
H H H F F
H H F

25
 Exercises
3. For each pair below, select the one with a smaller angle.
(a) PH3 vs NH3, (b) BF3 vs PF3, (c) NH3 vs NH4+ (d) BF4- vs
XeF4
.. .. ..
P F
N P
H H H B F
H H H F F F
F

F - F
.. H +
N B F Xe F
H N F
H H H F F
H H F

26
 Exercises
3. For each pair below, select the one with a smaller angle.
(a) PH3 vs NH3, (b) BF3 vs PF3, (c) NH3 vs NH4+ (d) BF4- vs
XeF4
.. .. ..
P F
N P
H H H B F
H H H F F F
F

F - F
.. H +
N B F Xe F
H N F
H H H F F
H H F

27
 Exercises
3. For each pair below, select the one with a smaller angle.
(a) PH3 vs NH3, (b) BF3 vs PF3, (c) NH3 vs NH4+ (d) BF4- vs
XeF4
.. .. ..
P F
N P
H H H B F
H H H F F F
F

F - F
.. H +
N B F Xe F
H N F
H H H F F
H H F

28
 Exercises
3. For each pair below, select the one with a smaller angle.
(a) PH3 vs NH3, (b) BF3 vs PF3, (c) NH3 vs NH4+ (d) BF4- vs
XeF4
.. .. ..
P F
N P
H H H B F
H H H F F F
F

F - F
.. H +
N B F Xe F
H N F
H H H F F
H H F

29
30
 Summary of last lecture

• Molecular shape and VSEPR model

 2. Valence Bond Theory
Molecules – groups of atoms linked together by chemical
bonds. e.g.
O
H H O C O
H 2O CO2

An ideal theory of molecular structure should be able to explain

at least the following:
* How chemical bonds are formed
* How many chemical bonds an atom can form
* Why a molecule adopts a particular shape
* Why a molecule has a particular properties

We have previously discussed the Lewis theory

Other theories we are going to introduce in this chapter are:
1. Valence bond theory
2. MO theory 32
 Valence Bond Theory
Valence Bond Theory: a theory describing covalent bond in
terms of the overlap of atomic orbitals.

Nature of the bond. The chemical bond is formed by an

overlap of atomic orbitals of two atoms so that the two orbitals
can be occupied by an electron pair. e. g.

H H
H2 + H H or H H

The electron density of shared electron

pair is a maximum between the bonded
atoms. The shared electron pair provided
the attractive force for the bonding
atoms. 33
 Comments on Bond Formation and
Types of Bonds.
A B A B
(a) Only atomic orbitals that
match with each other can +
overlap to form a bond. The
better the overlap, the
A B
stronger the bond. +

Will the following combinations lead to the formation of bond?

A B A B A B

+
+

34
 Comments on Bond Formation and
Types of Bonds.
A B A B
(a) Only atomic orbitals that
match with each other can +
overlap to form a bond. The
better the overlap, the
A B
stronger the bond. +

Will the following combinations lead to the formation of bond?

A B A B A B

+
+
Yes
35
 Type of Bonds
(b) Type of bonds: overlap of atomic orbitals can give chemical
bonds having different symmetry properties.

Based on symmetry properties, chemical bonds can be classified

into  and π bonds.

-bonds: symmetric around π-bonds: has one nodal plane

the internuclear axis. e.g. through the internuclear axis. e.g.
A B A B
A B A B
+
+

A A B A B
B A B
+ +

36
 Multiple Bonds
Single bonds are usually  bonds.

In a multiple bond, one of the bonds is a  bond and

the rest is/are  bonds.

One σ bond One σ bond plus One σ bond plus

one π bond two π bonds

37
 Why an Electron Pair?
Energy consideration:
The energy of the system is lowered when the two electrons of
the bonding pair are of opposite spin. e.g. in the case of H2.

38
 Number of Bonds Around an Atoms
• Since pairing up the
electrons lowers the energy,
atoms with unpaired H 3p
Cl
electrons tends to form 1s

chemical bonds to pair up 3s

the electrons.
Cl H Cl Cl

• An atom can form covalent

bonds with each of its
stable valence orbitals with
a single electron.
O O
O 2p
• # bonds = # unpaired e- (or O O
orbitals with unpaired e-) 2s
39
Valence Bond Theory and Molecular Geometry

The shape of the molecule is determined primarily by

the directional characteristics of the orbitals involved.
e.g.

H H
o
90 104o
O H O
H
predicted actually

40
 Hybridization and Molecular Shape
The needs of hybridization scheme:
(1) To explain the (2) To generate valence orbitals
shapes of molecules. containing unpaired electrons.
Be C
no hybridization B

O H O H
90o H 104o 2px 2py 2pz
2px 2py 2pz 2px 2py 2pz
H actually
theory 2s 2s 2s
If no hybridization
# of bond can be formed:
0 1 2
Reality 2 3 H 4
H
H Be H H B C
H
H H H
41
 Hybridization – Hybrid Orbitals
• Pauling proposed that atomic orbitals are hybridized before
forming chemical bonds.

• Hybridization of atomic orbitals gives hybridized atomic

orbitals (HAOs) with unique directional properties.

• Hybrid orbitals are mixtures of atomic orbitals with

intermediate energy

• n atomic orbitals will generate n hybrid orbitals.

For example, +
+
s,p hybridization
-
42
 Notes on Hybridization
* The number of required hybridized orbitals = number of
stereochemical electron pairs (lone pair + -bonding
electron pair)

e.g. How many HAOs are needed for the central atoms in
the following compounds?
..
H O
H Be H N
H H B P
H H Me
H Me Me

43
 Notes on Hybridization
* The number of required hybridized orbitals = number of
stereochemical electron pairs (lone pair + -bonding
electron pair)

e.g. How many HAOs are needed for the central atoms in
the following compounds?
..
H O
H Be H N
H H B P
H H Me
H Me Me

2 4 3 4

44
 Notes on Hybridization
The directional properties of the required HAOs depend
on the types of hybridization, which is related to the
geometry of the molecules. For example,

Geometry Required directional

properties of HAOs

45
 Common Hybridization Schemes
Hybridization schemes involving s and p orbitals:
Three possibilities

sp hybridize

px py pz

sp2 hybridize
s
z
y sp3 hybridize
x
46
 sp Hybridization

Required for
z
linear
y px py pz py pz
molecules,
x
e.g.
s sp hybridized orbitals
X Be X

+
+
-

47
 sp2 Hybridization
Required for
F
trigonal planar F B
molecules,
F
e.g.

z
y
pz
x
px py pz

sp2 hybridized orbitals

s
48
 sp2 Hybridization
Required for z
trigonal planar y
pz
molecules, x
e.g. px py pz
F
F B sp2 hybridized orbitals
F s

- +

- -

49
 sp3 Hybridization
H ..
Required for
tetrahedral C N
H H
molecules, e.g. H H H
H

z
y
x
px py pz

sp3 hybridized orbitals

s

50
 Hybridization involving d Orbitals
For geometries involving expanded octets on the central atom,
we must use d orbitals in our hybrids. For example,

d d orbital
E
sp3d hybridize
p
trigonal
bipyramid s sp3d orbital

d d orbital
E sp3d2 hybridize
p
octahedron s sp3d2 orbital
51
Hybrid Orbitals involving d Orbitals
F

E F P F
F
F
trigonal bipyramid

F
F
E F S F
F
F
octahedron

Pentagonal bipyramidal
Geometry (sp3d3) 52
Summary: Common Structures and HAO Patterns
number of idealized shape example HAO of
Stereochemical central atoms
distinct electron pair
2 E H Be H sp
linear
O C O

F
3 E
B sp2
trigonal plane F F

H
+ sp3
E N
4 H
H H
tetrahedron ..
N
H
H H 53
Summary: Common Structures and HAO Patterns
Number of idealized shape example HAO of
Stereochemical central atoms
distinct electron pair
F
5 F
E F P sp3d
F
trigonal bipyramid F

F
:
F I
:
F
F
F
6 E F S F sp3d2
F
octahedron F
..
F
F Xe F 54
F ..
 Exercises
1. Suggest the hybridization of the central atoms in:
a) Me3P=O b) XeF4 c) S(O)F4.

To determine the hybridization:

(i) Draw a Lewis structure, (ii) count the no. of stereochemical electron
pairs around central atom, (iii) geometry  hybridization scheme

55
 Exercises
1. Suggest the hybridization of the central atoms in:
a) Me3P=O b) XeF4 c) S(O)F4.

To determine the hybridization:

(i) Draw a Lewis structure, (ii) count the no. of stereochemical electron
pairs around central atom, (iii) geometry  hybridization scheme

Lewis structures
F
O
F
.. F
P F Xe F O S
.. F
Me F
Me
Me F

56
 Exercises
1. Suggest the hybridization of the central atoms in:
a) Me3P=O b) XeF4 c) S(O)F4.

To determine the hybridization:

(i) Draw a Lewis structure, (ii) count the no. of stereochemical electron
pairs around central atom, (iii) geometry  hybridization scheme

Lewis structures
F
O
F
.. F
P F Xe F O S
.. F
Me F
Me
Me F
sp3 sp3d2 sp3d
57
 Summary: Valence Bond Theory
1. A bond is formed by overlap of orbitals which is filled with a pair
of electrons.

2. # of bonds around an atom = # of unpaired electrons required

3. The geometry is determined by the directional properties of

orbitals.

1. AOs can hybridize to generate orbitals of required directional

properties.
2. The hybridized orbitals can be used to hold lone pairs and 
bonding electron pairs.
3. Type of hybridization is related to geometry [# of lone pairs,
bonds].

4. Valence electrons may need to be re-distributed to generate

enough unpaired electrons. 58
 Example. (a) Bonding in BeH2

(a) H Be H Be:1s22s2

Hybridization of Be:

# of bond around Be:

# unpaired e- needed for Be:

59
 Example. (a) Bonding in BeH2

(a) H Be H Be:1s22s2

Hybridization of Be: sp

# of bond around Be: 2

# unpaired e- needed for Be: 2

60
 Example.Exercises
(a) Bonding in BeH2

(a) H Be H Be:1s22s2

Hybridization of Be: sp

# of bond around Be: 2

# unpaired e- needed for Be: 2

Each of the sp orbital of Be can overlap with an s orbital of H to

form a Be-H bond.

H Be H 61
 Example. Bonding in BH3
H
(b) H B B: 2s22p1
H

Hybridization of B:

# of bond around B:

# unpaired e- needed for B:

62
 Example. Bonding in BH3

H
B: 2s22p1
(b) H B
H

Hybridization of B: sp2

# of bond around B: 3

# unpaired e- needed for B: 3

63
 Example. Bonding in BH3

H
(b) H B B: 2s22p1
H

Hybridization of B: sp2

# of bond around B: 3

# unpaired e- needed for B: 3

H
Each of the sp2 orbitals of B can
H B
overlap with an s orbital of H to form
a B-H bond. 64
H
 Example. Bonding in CF4
F
C: 2s22p2 F: 2s22p5
(c) C
F
F F

Hybridization of C:

# of bond around C:

# unpaired e- needed for C:

65
 Example. Bonding in CF4
F
C: 2s22p2 F: 2s22p5
(c) C
F
F F

Hybridization of C: sp3

# of bond around C: 4

# unpaired e- needed for C: 4

66
 Example. Bonding in CF4
F C: 2s22p2 F: 2s22p5
(c) C
F
F F

Hybridization of C: sp3

# of bond around C: 4

# unpaired e- needed for C: 4

Each of the sp3 orbitals of C can

overlap with a p or hybrid orbital
of F to form a C-F bond.

67
 ..
:F:
Question: In CF4, what is the hybridization of F? C
F
F F

Hybridization of F??

68
 ..
:F:
Question: In CF4, what is the hybridization of
F? C
F
F F
Hybridization of F??

F: 2s22p5
s p

sp p

sp2 p

sp3

69
 ..
:F:
Question: In CF4, what is the hybridization of
F? C
F
F F

Hybridization of F?? Hybridization is related to geometry.

F: 2s22p5 Since F is at terminal, it is hard to judge

s p its hybridization.

F can use a p, sp, sp2 or sp3 hybrid

sp p orbital with an unpaired e- to form bond
with C.

sp2 p Often, one choose a scheme for terminal

atoms such that __________________.

sp3
In CF4, we can assume that F is _______
hybridized. 70
 ..
:F:
Question: In CF4, what is the hybridization of
F? C
F
F F

Hybridization of F?? Hybridization is related to geometry.

F: 2s22p5 Since F is at terminal, it is hard to judge

s p its hybridization.

F can use a p, sp, sp2 or sp3 hybrid

sp p orbital with an unpaired e- to form bond
with C.

sp2 p Often, one choose a scheme for terminal

atoms such that the lone pairs are
equivalent or based on VSEPR model.
sp3
In CF4, we can assume that F is sp3
hybridized. 71
Hybridization of terminal atoms?
..
:Cl :
.. ..
.. O .. .. ..
H C N: :O :Cl.. .. I Cl
.. :
.. O
..
: Cl
.. :
Hybridization of terminal atoms?
..
:Cl :
.. ..
.. O .. .. ..
H C N: :O :Cl.. .. I Cl
.. :
.. O
..
: Cl
.. :

“2 p” “4 p” “3 p” “4 p”
sp sp3 sp2 sp3
 Exercises
1. Using valence bond theory, describe the bonding in the
following molecules:
(a) PH3 (b) SF6

(a) PH3 P: 3s23p3

Lewis structure:

Hybridization of P:

#of bond around P:

# unpaired e- needed for P:

74
 Exercises
1. Using valence bond theory, describe the bonding in the
following molecules:
(a) PH3 (b) SF6

(a) PH3 P: 3s23p3 ..

P
H H
Lewis structure: H

Hybridization of P: sp3

#of bond around P: 3

# unpaired e- needed for P: 3

75
 Exercises
1. Using valence bond theory, describe the bonding in the
following molecules:
(a) PH3 (b) SF6

(a) PH3 P: 3s23p3 ..

P
H
Lewis structure: H H 3s2 3p3
Hybridization of P: sp3 hybridization
#of bond around P: 3

# unpaired e- needed for P: 3 (sp3)5

P is sp3 hybridized.

One of the hybridized orbitals is occupied by the lone pair.

76
The other three combine with H's 1s orbitals to form three P-H bonds.
 Exercises

3s2 3p3
hybridization

(sp3)5

3p3 hybridization

3s2 (sp3)5

77
 Exercises
(b) SF6 S: 3s23p4 F: 2s23p5

Lewis structure:

Hybridization of S:

#of bond around S:

# unpaired e- needed for S:

78
 Exercises
(b) SF6 S: 3s23p4 F: 2s23p5
F
F
F S F
Lewis structure:
F
F
Hybridization of S: sp3d2

#of bond around S: 6

# unpaired e- needed for S: 6

79
 Exercises
(b) SF6 S: 3s23p4 F: 2s23p5
F
F
F S F
Lewis structure:
F 3s2 3p4 3d
F
promotion
Hybridization of S: sp3d2

#of bond around S: 6

3s 3p 3d
# unpaired e- needed for S: 6
hybridization

3d
(sp3d2)6
S is sp3d2 hybridized. Each of the hybridized orbitals combine with
a p or a hybrid orbital (e.g. sp3) of F to form a S-F bond
80
 Formation of Multiple Bonds
Single bonds are usually  bonds.

In a multiple bond, one of the bonds is a  bond and the rest is/are 
bonds.

 bonds are formed between un-hybridized p or d orbitals.

One σ bond One σ bond plus One σ bond plus

one π bond two π bonds

81
 Bonding in C2H4

• Ethylene has a double bond in its Lewis

H H
structure.
C C
• Carbon has a trigonal planar geometry H H

sp2

C is sp2 hybridized
82
C is sp2 hybridized. Two of the sp2 hybridized orbitals combine with
H's 1s orbital to form C-H  bonds. One of the sp2 hybridized
orbitals combine with an sp2 hybridized orbital of another C to form
the C-C  bond. The unhybridized p orbital combines with the
unhybridized p orbital of another C to form the C-C  bond. 83
 Bonding in Acetylene
• Acetylene has a triple bond in its
Lewis structure. H C C H
• It is a linear molecule.

sp

C is sp hybridized
84
Bonding in Acetylene H C C H
p

sp H
C C H
sp

Set of orbitals on C
(2sp + 2 p)

H
C C H

In acetylene, two sp orbitals form a  bond between the carbons, and

two pairs of p orbitals overlap in  fashion to form the two  bonds.
Two sp hybridized orbitals combine with H's 1s orbital to form the
two C-H  bonds.
85
 Exercises
1. Using valence bond theory to describe the bonding
in CO2.

86
 .. ..
Lewis structure: :O C O:
Hybridization of C: Hybridization of O:

#of bond around C: #of bond around O:

# unpaired e- needed for C: # unpaired e- needed for O:

C O
2s2 2p2 2s2 2p4

87
 .. ..
Lewis structure: :O C O:
Hybridization of C: sp Hybridization of O:

#of bond around C: 4 #of bond around O:

# unpaired e- needed for C: 4 # unpaired e- needed for O:

C O
2s2 2p2 2s2 2p4

88
 Exercises
.. ..
Lewis structure: :O C O:
Hybridization of C: sp Hybridization of O: sp2

#of bond around C: 4 #of bond around O: 2

# unpaired e- needed for C: 4 # unpaired e- needed for O: 2

O
C 2s2 2p4
2s2 2p2

89
 .. ..
Lewis structure: :O C O:
Hybridization of C: sp Hybridization of O: sp2

#of bond around C: 4 #of bond around O: 2

# unpaired e- needed for C: 4 # unpaired e- needed for O: 2

C
2s2 2p2 O
2s2 2p4
2s1 2p3
hybridization
hybridization

(sp) 2
2p 2 (sp2)5 2p1 90
 .. ..
Lewis structure: :O C O:
Hybridization of C: sp Hybridization of O: sp, sp2 or no

#of bond around C: 4 #of bond around O: 2

# unpaired e- needed for C: 4 # unpaired e- needed for O: 2

C C-O  bond O
2s2 2p2 2s2 2p4
O C O

2s1 2p3 C-O  bond hybridization

hybridization O O O
(sp2)5 2p1
91
(sp)2 2p2
 .. ..
Lewis structure: :O C O:
Hybridization of C: sp Hybridization of O: sp, sp2 or no

# of bonds around C: 4 # of bond around O: 2

# unpaired e- needed for C: 4 # unpaired e- needed for O: 2

C
2s2 2p2 C-O  bond O
2s2 2p4
O C O
2s1 2p3
C-O  bond hybridization
hybridization

O O O
(sp)2 (sp2)5 2p1
2p2

C and O are sp and sp2 hybridized, respectively. Two C-O  bonds

are formed by overlap of sp of C and sp2 orbital of O. Two C-O
perpendicular  bonds are formed by overlap of p orbitals of C and
O. 92

2
The Orbitals for CO2

93
93
 Summary of Last lecture

• Valence bond theory

 Weaknesses of the Valence Bond Theory:
• It cannot explain the formation of molecules with odd number of
electrons.
e.g. . ..
NO has 11e ’s
-
: N O : ??

• It cannot explain some of the physical properties.

For example,

O2, O 1s22s22p4

O=O VB Theory: 1 σ bond

1 π bond

The VB theory predicts that all the electrons in O 2 are paired up,
but experiments show that there are two unpaired electrons in
the molecule. 95
 3. Molecular Orbital Theory
Basic concepts of Molecular Orbital Theory

(1) Electrons in an atom are in atomic orbitals. Electrons

in a molecule are in molecular orbitals.

The electrons are spread over all the atoms in a

molecule and bind the nuclei together into a stable
unit.

V. B. Localized bond
MO, delocalized bond 96
 Basic Concepts of Molecular Orbital Theory

(2) How to obtain molecular orbitals?

Molecular orbitals (MOs) are obtained by linear

combination of atomic orbitals (LCAO).

Atomic orbitals with the same symmetry, and similar

energy can combine to give molecular orbitals.

N atomic orbitals combine to give N molecular orbitals

Since inner shell electrons are usually localized, we usually

just consider the valence shell electrons and their orbitals.
e.g.

F: 1s22s22p5  only 2s22p5 are considered.

97
 Example: Bonding of H2
Atomic orbitals
Molecular Orbitals of H2:
Ha Ha
2 1s ==> 2 MOs
Ha Hb
1s(Ha) 1s(Hb)

According to
symmetry: MO1 and
MO2 are both σ type
orbitals, and are
labelled as σ and σ*,
respectively.

98
 Relative Energies of MOs
• It can be shown that E1 > E2
H H
*
• The energy of the  orbital is
E1
lower than that of atomic 1s
orbital

E2 1s • The energy of the orbital is

1s higher than that of atomic 1s
orbital.
H H 
• An occupied σ orbital forms a σ
bond.

99
 Types of Bonding/Antibonding
Interactions:
 bonding/antibonding interactions:
*2s
e.g. A B A-B
+

2s 2s 2s
A+B
A B

 bonding/antibonding interactions:
A B A-B *2px
e.g.
+
A+B 2px
px px
A B 100
 Comments on Bond Formation

Only atomic orbitals that *2s

A B A-B
match with each other can
overlap to form a bond. +
The better the overlap, the 2s 2s
2s A+B
stronger the bonds.
A B

A B B
A
+
s pz +
A B

A B
101
 Comments on Bond Formation
Combination of AOs to form MOs is also called orbital interaction.

Strong orbital interaction allows:

– a larger raise/lowering in energies of bonding/antibonding MOs.

– a stronger bond when the bonding MO is occupied.

Strong orbital interaction: Weak orbital interaction:

antibonding MO antibonding MO

AO(1)

AO(1) AO(2)
AO(2)

bonding MO bonding MO

How to achieve a strong orbital interaction?

• Effective orbital overlap. 102
• AOs are close in energy.
 Filling the Molecular Orbitals with
Electrons
*1s
Each molecular orbital may be
occupied by two electrons with
paired spins. Electrons are
filled to a molecular orbital of 1s
1s
low energy first, as in filling
1s
atomic orbitals. e.g. H2

Bond order = ½ (bonding electrons – antibonding electrons)

e.g. Bond orders of H2 = ½ (2 – 0) =1

Electronic configuration: arrangement of electrons in molecules

e.g. Electronic configuration of H2: (1s)2

103
Note: Stable species should have a bond order larger than zero.
 Exercises
1. Are He2 and He2+ stable?

He2: *1s He2+: *1s

1s 1s
1s 1s
1s 1s
Electron configuration:
Electron configuration:
Bond order = Bond order =

Energy level diagram: Diagram showing the energy

levels of MOs and how they are filled with electrons. 104
 Exercises
1. Are He2 and He2+ stable?

He2: *1s He2+: *1s

1s 1s
1s 1s
1s 1s
Electron configuration: (1s)2(*1s)2
Electron configuration:
Bond order = (2 – 2)/2 = 0 Bond order =
Unstable

Energy level diagram: Diagram showing the energy

levels of MOs and how they are filled with electrons. 105
 Exercises
1. Are He2 and He2+ stable?

He2: *1s He2+: *1s

1s 1s
1s 1s
1s 1s
Electron configuration: (1s)2(*1s)2
Electron configuration: (1s)2(*1s)1
Bond order = (2 – 2)/2 = 0 Bond order = (2 – 1)/2 = 0.5
Unstable Stable

Energy level diagram: Diagram showing the energy

levels of MOs and how they are filled with electrons. 106
General Procedures to Obtain a MO Energy
Level Diagram

(1) Determine AOs that are available for making MOs.

(2) Determine which AOs can combine to form MOs

(3) Determine relative E of MOs

(4) Draw the energy levels.

(5) Fill the MOs with e-.

107
 Summary of Last lecture
MO theory
(1) Electrons in a molecule are in molecular orbitals. *1s

(2) Molecular orbitals (MOs) are obtained by linear 1s

1s
1s
combination of proper atomic orbitals.

(3) Each MO may be occupied by two electrons. Electrons are

filled to a MO of low energy first

Some terminologies:
Bonding MO (, ,), antibonding MO (, , bond order,
electron configuration, MO energy level diagram.
2. Homo-nuclear Diatomic Molecules (X2)
of Second Period Elements
Construction of MO energy levels.
AOs available for making MOs and possible orbital combination?
x

X X z

y
X X

2px 2py 2pz 2px 2py 2pz

109
2s 2s
Possible Orbital Interactions
X X

2px 2py 2pz 2px 2py 2pz

2s 2s

110
Possible Orbital Interactions
X X

2px 2py 2pz 2px 2py 2pz

2s 2s

111
 Possible Orbital Interactions

X X X X

2px 2py 2pz 2px 2py 2pz 2px 2py 2pz 2px 2py 2pz

2s 2s 2s 2s

Since the energy of p is much higher than s, the s/p

interaction is less significant than p/p or s/s interactions.
To a first approximation, we can neglect the s/p
interaction. 112
 Possible Orbital Interactions

X X X X

2px 2py 2pz 2px 2py 2pz 2px 2py 2pz 2px 2py 2pz

2s 2s 2s 2s

Since the energy of p is much higher than s, the s/p

interaction is less significant than p/p or s/s interactions.
To a first approximation, we can neglect the s/p
interaction.
113
 Shapes and Energies of MOs
We have the following MOs:
*2s
A B A-B
+

2s 2s 2s
A+B
A B

*2pz
A B A+B
+
pz pz A-B 2pz
A B

114
 Shapes and Energies of MOs

A B A-B *2px Are π2px and π2py of

+ the same energy?
A+B 2px
px px

A B

*2py
A B

+
2py
py py
A B

115
 Shapes and Energies of MOs

A B A-B *2px Are π2px and π2py of

+ the same energy?
A+B 2px
px px

A B
Yes, π2px and π2py
are of the same
*2py
energy.
A B

+ π*2px and π*2py are

2py of the same energy.
py py
A B

116
Which interaction is stronger?

A B A-B *2px

+
A+B 2px
px px

A B

*2pz
A B A+B
+
pz pz A-B 2pz
A B

117
Which interaction is stronger?

A B A-B *2px

+
A+B 2px
px px

A B

*2pz
A B A+B
+
pz pz A-B 2pz
A B

pz/pz interaction is stronger than px/px interaction.

118
 Orbital Energy Levels
Possible interactions:
X X

2px 2py 2pz 2px 2py 2pz

2s 2s

119
 Orbital Energy Levels
σ*
2p 2p
Possible interactions:
X X *2p
2px 2py 2pz 2px 2py 2pz
2p
2px 2py 2pz 2px 2py 2pz
2p

*2s

2s 2s
2s 2s

X 2s
X

The energy level diagram is

suitable for F2, and O2, but not for
species such as N2, C2, B2, Li2.
120
 Orbital Energy Levels
For species such as N2, C2, B2, Be2, Li2, the energy levels are
shown below.
σ*
2p 2p

• σ2p is of higher
*2p
energy than π2p
2px 2py 2pz 2p because of the
2px 2py 2pz mixing of s and
2p p orbital.

*2s • Detailed
explanation is
out of scope for
this course.
2s 2s

X 2s 121
X
Molecular Orbitals. Summary of
Second Row Diatomic Molecules

122
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic?
2p

*2p
2px 2py 2pz 2px 2py 2pz
2p
2p

*2s

2s 2s

2s
123
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic? 2p

*2p

2px 2py 2pz 2p 2px 2py 2pz

2p

*2s

2s 2s

X 2s
X 124
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic? MO energy level for Li2 and B2
2p
Li2:
Total # of valence e-: *2p
Electronic config.: 2p
2px 2py 2pz 2px 2py 2pz
Bond order:
2p

*2s
B 2:
Total valence e-:
2s 2s
Electronic config.:
Bond order:
X 2s 125
X
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic? MO energy level for Li2
2p
Li2:
Total # of valence e-: 2e- *2p
Electronic config.: (2s)2
2px 2py 2pz 2p 2px 2py 2pz
Bond order: (2 – 0)/2 = 1
2p
No unpaired e-, thus Li2 is diamagnetic
*2s
B 2:
Total valence e-:
2s 2s
Electronic config.:
Bond order:
X 2s 126
X
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic? MO energy level for B2
2p
Li2:

Total # of valence e-: 2e- *2p

Electronic config.: (2s)2
2px 2py 2pz 2p 2px 2py 2pz
Bond order: (2 – 0)/2 = 1
2p
No unpaired e-, thus Li2 is diamagnetic
*2s
B 2:
Total valence e-: 6e-
2s 2s
Electronic config.: (2s)2(*2s)2(2p)2
Bond order: (4–2)/2 = 1
Two unpaired e-’s, thus B2 is paramagnetic X 2s 127
X
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic?
MO energy level for O2 and F2
O 2: 2p
Total # of valence e-:
Electronic config.: *2p
Bond order:
2px 2py 2pz 2px 2py 2pz
2p
2p

F2: *2s
Total valence e-:
Electronic config.:
2s 2s
Bond order:
2s 128
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic?
MO energy level for O2
O 2: 2p
Total # of valence e-: 12e-
Electronic config.:
*2p
(2s)2(*2s)2(2p)2(2p)4(*2p)2
Bond order: (8 – 4)/2 = 2 2px 2py 2pz 2px 2py 2pz
2p
Two unpaired e-, thus O2 is paramagnetic
2p
F2: *2s
Total valence e-:
Electronic config.:
Bond order: 2s 2s

2s 129
 Exercises
1. Consider Li2, B2, O2 and F2
(a) Give the electronic configuration and the bond order for each
species.
(b) which of them are paramagnetic?
O 2: MO energy level for F2
2p
Total # of valence e-: 12e-
Electronic config.:
(2s)2(*2s)2(2p)2(2p)4(*2p)2 *2p
Bond order: (8 – 4)/2 = 2 2px 2py 2pz 2px 2py 2pz
2p
Two unpaired e-, thus O2 is paramagnetic
2p
F2: *2s
Total valence e-: 14e-
Electronic config.:
(2s)2(*2s)2(2p)2(2p)4(*2p)4 2s 2s

Bond order: (8–6)/2 = 1

2s 130
No unpaired e-’s, thus F2 is diamagnetic
 Summary of Last lecture
• MO of Homo-nuclear Diatomic Molecules (X2) of Second
Period Elements

2p
2p

*2p
*2p 2p
2px 2py 2pz 2px 2py 2pz
2px 2py 2pz 2px 2py 2pz
2p
2p
2p *2s
*2s
2s 2s

2s 2s

X 2s
X
2s

For F2 and O2 For other X2

 Exercises
2. Which species has a stronger O-O bond, O2 or [O2]2+?

O2: total valence e- =

[O2]2+: total valence e- =

Bond order of O2 =

Bond order of [O2]2+ =

132
 Exercises
2. Which species has a stronger O-O bond, O2 or [O2]2+?

O2: total valence e- = 2p

*2p
[O2]2+: total valence e- = 2px 2py 2pz 2px 2py 2pz
2p
2p
Bond order of O2 =
*2s

Bond order of [O2]2+ = 2s

2s

2s

133
 Exercises
2. Which species has a stronger O-O bond, O2 or [O2]2+?

O2: total valence e- = 12e- 2p

*2p
[O2]2+: total valence e- = 2px 2py 2pz 2px 2py 2pz
2p
2p
Bond order of O2 = (8-4)/2 = 2
*2s

Bond order of [O2]2+ = 2s 2s

2s
MO energy level for O2
134
 Exercises
2. Which species has a stronger O-O bond, O2 or [O2]2+?

O2: total valence e- = 12e- 2p

*2p
[O2]2+: total valence e- = 10e- 2px 2py 2pz 2px 2py 2pz
2p
2p
Bond order of O2 = (8-4)/2 = 2
*2s

Bond order of [O2]2+ = (8-2)/2 = 3 2s

2s

[O2]2+ has a stronger O-O bond. 2s

MO energy level for [O2]2+
135
3. Hetero-nuclear Diatomic Molecules
Orbital interactions involving homo-nuclear diatomic molecules:

H H antibonding orbital

Starting AOs have

the same energy

A and B have equal

contribution to the
bonding and
antibonding MOs.
bonding orbital
H H

136
3. Hetero-nuclear Diatomic Molecules
Orbital interactions involving hetero-nuclear diatomic molecules:

A B The antibonding MO
has more contribution
• Starting AOs from A.
have different
energy
A
• A and B have
un-equal
contribution to
the bonding and B
antibonding The bonding MO has
MOs. more contribution
A B from B.

137
Example. MO Energy Level Diagrams for
NO, CN-
• The atoms involved are similar as they are adjacent to each other in
the periodic table.
• We can use a diagram similar to that of homodiatomic species

Homodiatomic species Heterodiatomic species

2p 2p

*2p *2p
2px 2py 2pz
2px 2py 2pz 2p
2px 2py 2pz 2px 2py 2pz
2p 2p
2p
*2s
*2s

2s
2s 2s
2s

X X'
2s 2s
X X 138
X = Li, B, C, N
 Exercises
1. The bond order in the NO molecule is
a) 1 b) 1.5 c) 2 d) 2.5 e) 3

139
 Exercises
1. The bond order in the NO molecule is
a) 1 b) 1.5 c) 2 d) 2.5 e) 3

# V. E. = 5 (N) + 6 (O) =
11

140
 Exercises
1. The bond order in the NO molecule is
a) 1 b) 1.5 c) 2 d) 2.5 e) 3

2p
# V. E. = 5 (N) + 6 (O) =
11 *2p
2px 2py 2pz
2px 2py 2pz
2p
2p
B. O. = ½ (8- 3) = 2.5
*2s

2s
2s

N O
2s
141