Prof. Dr.

Mohamed Mansour El-bendary

Prof. of Inorganic Chemistry
Chemistry Department, Faculty of Science, University of Jeddah
1
 Valence Bond Theory

• Valence bond theory is an approximate theory to explain the

covalent bond from a quantum mechanical view.

– According to this theory, a bond forms

between two atoms when the following
conditions are met.
(See Figures 1 and 2)
1. Two atomic orbitals “overlap”
2. The total number of electrons in both
orbitals is no more than two.
Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 10–2
 Figure 1: Bonding in HCl

Presentation of Lecture Outlines, 10–3

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 Valence Bond Theory (VBT)

Bonding occurs only by the outermost shells (valence shells) in the

interacting atoms. According to this theory a covalent bond is formed
between the two atoms by the overlap of half filled valence atomic orbitals
of each atom containing one unpaired electron. Because of the overlapping,
it is most probable that bonding electron pairs should be concentrated into
region of space between the bonded atoms (the bond region). The strength
of the bond depends on the amount of overlap; the greater the overlap of
the orbitals the stronger the bond. Also remember that the two overlapping
orbitals can not hold more than two electrons and their spins must be
opposite. The overlapping atomic orbitals can differ. The two types of
overlapping orbitals are sigma and pi. Sigma bonds occur when the orbitals
of two shared electrons overlap head-to-head. Pi bonds occur when two
orbitals overlap when they are parallel.
 Potential energy diagram for the
formation of hydrogen molecule (H2)

• At large distances the energy is zero; meaning "no

interaction". As the internuclear distance decreases the
attractive force dominates and the potential energy decreases
till it reaches minimum value, then after the repulsive force
dominates and the potential energy increases again; Figure 1.
The attractive and repulsive forces are balanced at the
minimum point in the curve. The internuclear distance at
which the energy is minimum defines the bond length. This is
more correctly known as the equilibrium bond length because
the thermal motion causes the two atoms to vibrate about this
distance. The bond energy which is the energy required to
break the bond is equal to the depth of the well of the
potential energy curve; Figure 1.
Presentation of Lecture Outlines, 10–5
Potential energy diagram for the formation of
hydrogen molecule (H2) Fig 2

Presentation of Lecture Outlines, 10–6

 Hybrid Orbitals
• One might expect the number of bonds formed
by an atom would equal its unpaired electrons.
– Chlorine, for example, generally forms
one bond and has one unpaired
electron.
– Oxygen, with two unpaired electrons,
usually forms two bonds.
– However, carbon, with only two
unpaired electrons, generally forms
four bonds. For example, methane,
CH4, is well known.
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 Hybrid Orbitals

• The bonding in carbon might be explained as follows:

– Four unpaired electrons are formed as an

electron from the 2s orbital is promoted
(excited) to the vacant 2p orbital.
– The following slide illustrates this
excitation.
– More than enough energy is supplied for
this promotion from the formation of two
additional covalent bonds.

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 2p 2p

2s 2s
Energy

1s 1s
C atom (ground state) C atom (promoted)
 Hybrid Orbitals

• One bond on carbon would form using the 2s orbital

while the other three bonds would use the 2p orbitals.

– This does not explain the fact that the four

bonds in CH4 appear to be identical.
– Valence bond theory assumes that the four
available atomic orbitals in carbon combine
to make four equivalent “hybrid” orbitals.

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 Hybrid Orbitals

• Hybrid orbitals are orbitals used to describe bonding

that are obtained by taking combinations of atomic
orbitals of an isolated atom.

– In this case, a set of hybrids are

constructed from one “s” orbital and three
“p” orbitals, so they are called sp3 hybrid
orbitals.
– The four sp3 hybrid orbitals take the shape
of a tetrahedron (See Figure 10.23).
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You can represent the hybridization of carbon in
CH4 as follows.

2p
sp3 sp3
C-H bonds
2s
Energy

1s 1s 1s
C atom C atom C atom
(ground state) (hybridized state) (in CH4)
 Hybrid Orbitals

• Note that there is a relationship between the type of

hybrid orbitals and the geometric arrangement of
those orbitals.

– Thus, if you know the geometric

arrangement, you know what hybrid
orbitals to use in the bonding description.
– Figure 10.24 summarizes the types of
hybridization and their spatial
arrangements.
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 Hybrid Orbitals

• To obtain the bonding description of any atom in a

molecule, you proceed as follows:

5. Form bonds to this atom by overlapping

singly occupied orbitals of other atoms
with the singly occupied hybrid orbitals
of this atom.

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 Kinds of Hybrid Orbitals
Hybrid Geometric Arrangements Number Example
Orbitals of
Orbitals
sp Linear 2 Be in BeF2
(See Animation: sp Hydridization)

sp2 Trigonal planar 3 B in BF3

(See Animation: sp2 hydridization)

sp3 Tetrahedral 4 C in CH4

(See Animation: sp3 Hydridization)

sp3d Trigonal bipyramidal 5 P in PCl5

sp3d2 Octahedral 6 S in SF6
 Sp Hybridization, BeF2

E. S. of Be atom in ground
state 1s 2s 2p
E. S. of Be atom in excited state
1s 2s 2p
E. S. of Be atom in BeF2
molecule. Be atom have gained
two electrons from fluorine
atoms in BF2 molecule sp hybridization
 Sp2 Hybridization, BF3

E. S. of B atom in ground state

1s 2s 2p

E. S. of B atom in excited state

1s 2s 2p

E. S. of B atom in BF3 molecule.

Boron atom has gained three sp2 hybridization

electrons from fluorine atoms in BF3

Structure of BF3 molecule

 Sp3 Hybridization, BF4-

E. S. of B atom in BF3 molecule. 1s 2s 2p

Boron atom have gained three
electrons from fluorine atoms in sp2 hybridization
BF3 molecule

BF3 molecule has gained a lone

sp3 hybridization
pair from F- becoming a BF4- ion

Fluoroborate ion
tetrahedral
 Sp3 Hybridization, NH3
Electronic structure of the nitrogen 1s 2s 2p
atom - ground slate
Nitrogen atom has gained three electrons
from three H atoms in NH3 molecule
sp3 hybridization
The shape is either pyramidal or tetrahedral
with one corner occupied by lone pair, so
the molecule must be angular in shape with
angle 106o 45

Pyramidal

Structure of NH3 molecule

 Sp3 Hybridization, H2O

2p
sp3 sp3

lone O-H
2s pairs bonds
Energy

1s 1s 1s

O atom O atom O atom

(ground state) (hybridized state) (in H2O)
 Sp3 Hybridization, H2O
The shape of water molecule is either tetrahedral with
two corner occupied by two lone pairs or bent , so the
lone pairs distort the bond angle more than in ammonia
give angle 104o 27.

Bent
Structure of H2O molecule
 Sp3d Hybridization, PCl5

E. S. of P atom in ground
state 3s 3p 3d
E. S. of P atom in excited
state 3s 3p 3d
Phosphorus has gained
five electrons from
chlorine atoms in PCl5 sp3d hybridization

molecule

There are five orbitals in the outer shell

which are hybridized, giving five sp3d
hybrid orbitals and a trigonal bipyramid
arrangement.
Phosphorus pentachloride molecule
 Sp3d Hybridization, SF4
E. S. of S atom in
ground state 3s 3p 3d

E. S. of S atom in excited
state 3s 3p 3d

has gained four electrons

from fluorine atoms in sp3d hybridization
SF4 molecule

There are five orbitals in the outer shell

which are hybridized, giving five sp3d
hybrid orbitals and a trigonal bipyramid
arrangement. Four orbitals contain bond
pairs and two contain lone pairs giving
Seesaw-shape using the VSEPR model. The
bond angle are distorted from ideal 90,120
Sulphur tetraflouride molecule
 Sp3d Hybridization, ClF3
E. S. of Cl atom in
ground state 3s 3p 3d
E. S. of Cl atom in
excited state 3s 3p 3d
chlorine has gained three
electrons from fluorine
sp3d hybridization
atoms in ClF3 molecule
There are five orbitals in the outer shell which are hybridized,
giving five sp3d hybrid orbitals and a trigonal bipyramid
arrangement. Three orbitals contain bond pairs and two contain
lone pairs giving T-shape using the VSEPR model
 Sp3d Hybridization, I3‾
I2 + I‾ → I3‾
E. S. of I atom in ground state
5s 5p 5d

I atom has gained one electron

from another iodine atom in the
sp3 hybridization
12 molecule

Iodine has gained pair of

electrons from iodide ion thus
sp3d hybridization
forming the I3‾ ion

There are five orbitals in the outer shell

which are hybridized, giving five sp3d
hybrid orbitals and a trigonal bipyramid
arrangement. Two orbitals contain bond
pairs and three contain lone pairs giving
linear using the VSEPR model, angle 180o.
The tri-iodide ion (I3‾)
 Sp3d2 Hybridization, SF6
E. S. of S atom in ground
state 3s 3p 3d

E. S. of S atom in excited
state 3s 3p 3d

has gained six electrons from

fluorine atoms in SF6
sp3d2 hybridization
molecule

Sp3d2 hybridization occurs and the

six hybrid orbitals are directed to the
corners of a regular octahedron, 90o

Sulphur hexafluoride molecule

 A Problem to Consider

• Describe the bonding in XeF4 using hybrid

orbitals.
– From the Lewis formula for a molecule,
determine its geometry about the central
atom using the VSEPR model.

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 A Problem to Consider

• Describe the bonding in XeF4 using hybrid orbitals.

– The Lewis formula of XeF4 is

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 A Problem to Consider

• Describe the bonding in XeF4 using hybrid orbitals.

– From this geometry, determine the

hybrid orbitals on this atom,
assigning its valence electrons to
these orbitals one at a time.

Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 10–29
 A Problem to Consider

• Describe the bonding in XeF4 using hybrid orbitals.

– The xenon atom has four single bonds

and two lone pairs. It will require six
orbitals to describe the bonding.
– This suggests that you use sp3d2 hybrid
orbitals on xenon.

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 A Problem to Consider

• Describe the bonding in XeF4 using hybrid orbitals.

– Each Xe-F bond is formed by the overlap of

a xenon sp3d2 hybrid orbital with a singly
occupied fluorine 2p orbital.
– You can summarize this as follows:

Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 10–31
 Sp3d2 Hybridization, XeF4

5d

5p

5s
Xe atom (ground state)
 Sp3d2 Hybridization, XeF4

5d

sp3d2

Xe atom (hybridized state)

 Sp3d2 Hybridization, XeF4

5d

sp3d2

lone pairs Xe-F bonds

Xe atom (in XeF4)
Sp3d2 hybridization occurs. Four orbitals contain bond pairs and two
contain lone pairs giving square planar shape using the VSEPR model
 Multiple Bonding

• According to valence bond theory, one hybrid orbital

is needed for each bond (whether a single or
multiple) and for each lone pair.

– For example, consider the molecule

ethene.

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 Multiple Bonding

• Each carbon atom is bonded to three

other atoms and no lone pairs, which
indicates the need for three hybrid
orbitals.
– This implies sp2 hybridization.
– The third 2p orbital is left unhybridized
and lies perpendicular to the plane of the
trigonal sp2 hybrids.
– The following slide represents the sp2
hybridization of the carbon atoms.

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 (unhybridized,
2p 2p pi bond)

sp2
2s
Energy

1s 1s
C atom (ground state) C atom (hybridized)
 sp2 hybridization C2H4

E. S. of C atom in ground state

1s 2s 2p

E. S. of C atom in excited state

1s 2s 2p

−bond
Carbon has gained four electrons in
atoms in C2H4 molecule sp2 hybridization
 Multiple Bonding

• To describe the multiple bonding in ethene, we must

first distinguish between two kinds of bonds.

– A  (sigma) bond is a “head-to-head”

overlap of orbitals with a cylindrical shape
about the bond axis. This occurs when two
“s” orbitals overlap or “p” orbitals overlap
along their axis.
– A  (pi) bond is a “side-to-side” overlap of
parallel “p” orbitals, creating an electron
distribution above and below the bond axis.
(See Animation: Carbon-Carbon Double Bond)
Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 10–39
 Multiple Bonding

• Now imagine that the atoms of ethene move

into position.
– Two of the sp2 hybrid orbitals of each carbon
overlap with the 1s orbitals of the hydrogens.
– The remaining sp2 hybrid orbital on each
carbon overlap to form a  bond.

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 Multiple Bonding

• The remaining “unhybridized” 2p orbitals on each of

the carbon atoms overlap side-to-side forming a 
bond.

– You therefore describe the carbon-carbon

double bond as one  bond and one  bond.

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 Figure 10.26: Bonding in Ethylene

Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 10–42
 Multiple Bonding,CH CH
E. S. of C atom in ground state 1s 2s 2p

E. S. of C atom in excited state 1s 2s 2p

−bonds
Carbon has gained four electrons in
atoms in C2H2molecule sp hybridization

There is two -bond and two-bonds in

each carbon, -orbitals are not
hybridized, and do not affect the shape
of the molecule. The two sp hybrid
orbitals produced result in linear
carbons, with H-C-H angle of 180°.

What is the structure of SO2, SO3?

Structure of acetylene
Example: HCCH
The carbon dioxide molecule CO2, sp hybridization
O C O
E. S. of C atom in ground state
1s 2s 2p
E. S. of C atom in excited state

1s 2s 2p
−bonds
Carbon has gained four electrons from
two oxygen atoms in CO2 molecule
sp hybridization

There are two -bonds and two -bond in the molecule, -

orbitals are not hybridized, and do not affect the shape of
the molecule. Thus two electron pairs are reserved for -
orbitals. The remaining s and p orbitals are used the form
the -bands, and the two sp hybrid orbitals produced result
in a linear molecule, with a bond angle of 180°.
Presentation of Lecture Outlines, 10–45
The sulphur dioxide molecule SO2, sp2 hybridization

E. S. of S atom in ground
state
3s 3p 3d
E. S. of S atom in excited
state
3s 3p 3d
Sulphur has gained four
electrons from two
oxygen atoms in SO2 sp2 hybridization −bonds
molecule
The two electron pairs which form the  - O
bonds are excluded from hybridization, and
the resultant sp2 hybridization results in a S
planar triangular structure for the molecule
O
with one corner occupied by a lone pair and
the other two corners by oxygen atoms
Presentation of Lecture Outlines, 10–46
The sulphur trioxide molecule SO3, sp2 hybridization

E. S. of S atom in ground
state
3s 3p 3d
E. S. of S atom in excited
state
3s 3p 3d
Sulphur has gained six
electrons from three
oxygen atoms in SO3
sp2 hybridization −bonds
molecule

O
S
O O
Presentation of Lecture Outlines, 10–47
 Molecular Orbital Theory

• Two atomic orbitals combine to form

¯ a bonding molecular orbital
¯ an anti-bonding molecular orbital
• e- in bonding MO’s = stability
• e- in anti-bonding MO’s = instability
• # atomic orbitals combined equals #
of molecular orbitals formed

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 Molecular Orbital Theory

• For example, when two hydrogen atoms bond, a 1s

(bonding) molecular orbital is formed as well as a 1s *
(antibonding) molecular orbital.
(See Animation: s Orbitals/Bonding and Anti-Bonding)

– The following slide illustrates the relative

energies of the molecular orbitals compared
to the original atomic orbitals.
– Because the energy of the two electrons is
lower than the energy of the individual atoms,
the molecule is stable.
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 Rules of Molecular Orbitals

Rules for forming bonding and antibonding Mos

number of total molecular orbitals = number of total
atomic orbitals
atomic orbitals have the right symmetry
atomic orbitals overlap well
atomic orbitals have similar energy

Rules for filling electrons are the same for MOs and AOs.
start filling from the lowest energy orbital
follows Pauli exclusion principle and Hund's rule
Provides molecular energy information
Explains magnetic behavior
The more overlap between AOs the lower the energy of the
bonding orbital they create and the higher the energy of
the antibonding orbital
Presentation of Lecture Outlines, 10–50
s-s combination of atomic orbitals

Presentation of Lecture Outlines, 10–51

 Moleculuar Orbital (MO) Theory

These two new orbitals have ANTBONDING

different energies.

BONDING

The wave functions of hydrogen atom A and hydrogen atom B can

interact either constructively or destructively.
The one that is lower in energy is called the bonding orbital,
The one higher in energy is called an antibonding orbital.
Energy level diagrams / molecular
orbital diagrams
 Predicting Stability: H2+ & H2-
There is some stabilization, so it can be detected spectroscopically.
bond order = 1/2(1-0) = 1/2 bond order = 1/2(2-1) = 1/2

+ H2- has some

H2 has some 
 stability
stability

1s 1s 1s 1s

AO of AO of AO of
AO of H -
H  H H  configuration
configuration is is (1s)2(1s)1
MO of (1s)1 MO of
H 2+ H 2-
 Helium: He2+ vs He2

*1 *1
s s
Energy

Energy
1s 1 1s 1
s s

1s 1s
AO MO of AO AO MO of AO
of He He+ of of He He2 of He
He+

He2+ bond order = ½ present He2 bond order = 0, not exist

 Next Row: 2s & 2p orbitals

* *
2s 2s

2s 2s
Energy

Li2 Bonding in s-block Be2

2s homonuclear 2s
diatomic
molecules.
* *1
1s s

1s 1s

Li2 B.O. = 1 Be2 B.O. = 0

1s 1s
 MOs from 2p atomic orbitals

1- sigma bond
 through overlap
of orbitals along
the internuclear
axis.

2- pi bonds
through overlap
of orbitals above
 and below (or to
the sides) of the
internuclear axis.
Interactions between the 2s and 2p orbitals
> half filled p orbitals (O, F, Ne) energy 2p < 22p < 1*2p < 2*2p
 half filled p orbitals (B, C, N) energy 22p < 2p < 2*2p < 1*2p

The 2s and 2p

molecular orbitals
interact with each
other so as to
lower the energy
of the 2s MO and
raise the energy
of the 2p MO.
Relative Energy Levels for 2s & 2p

WITHOUT big WITH big 2s-2p

2s-2p repulsion repulsion

MO energy levels MO energy levels

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

• The term bond order refers to the number of bonds

that exist between two atoms.

– The bond order of a diatomic molecule is

defined as one-half the difference between
the number of electrons in bonding orbitals,
nb, and the number of electrons in
antibonding orbitals, na.

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 C. Bond Order -

Bond Order = ½(#bonding electrons -

# antibonding electrons)
 (s)2 B.O. = 1/2(2 - 0) = 1

 + (s)1 B.O. = 1/2(1 - 0) = 1/2

− (s)2(1s*)1 B.O. = 1/2(2 - 1) = 1/2

He2+ (s)2(1s*)1 B.O. = 1/2(2 - 1) = 1/2

He2 (s)2(1s*)2 B.O. = 1/2(2 - 2) = 0

2/6/2025
 The arrows show
the occupation of
molecular orbitals
by the valence
electrons in N2.

The molecular electron

N≡N configuration for N2
would be:

σ2s2σ*2s2π2p4σ2p2
Bond order =
(8-2)/2 = 3
 Let’s Practice!

What is the molecular configuration of an

O2 molecule?
How many total valence electrons
in the molecule?
12
Using Fig. 10.34 fill in the molecular
orbitals from the bottom up with the 12
total valence electrons.
σ2s2 σ*2s2 σ2p2 π2p4 π*2p2 Bond order O=O
= (8-4)/2=2
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MO Diagram for O2
 Let’s Practice!

What is the molecular configuration of an

F2 molecule?
How many total valence electrons
in the molecule?

14
Using Fig. 10.34 fill in the molecular
orbitals from the bottom up with
the 14 total valence electrons.
σ2s2σ*2s2 σ2p2 π2p4 π*2p4 Bond order F-F
= (8-6)/2=1
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For B2, C2, and N2 the interaction is so strong that
the 2p is pushed higher in energy than 2p orbitals
 Electronic Configurations of
Diatomic Molecules

• In heteronuclear diatomic molecules, such as CO or

NO, we must have additional molecular orbitals.

– The overlap of “p” orbitals results in two

sets of  orbitals (two bonding and two
antibonding) and one set of  orbitals
(one bonding and one antibonding).
(See Animation: Pi Bond and Antibond).
– The next slide illustrates the relative
energies of these molecular orbitals.
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 Let’s Start Slowly: HF

• Valence electrons
¯ H – 1s1
¯ F – 1s2 2s2 2p5
• Focus on the valence interactions
• Accommodate for differences in
electronegativity
• Allow mixing between symmetry-
allowed states
 Let’s Start Slowly: HF



Energy

1
s

2px 2py 2p


AO MO of AO
of H HF of F
 The MO diagram for NO

*2s

*2p
Energy

2p possible Lewis
2p 2p structures
0 0
2p
N O

*2s -1 +1

2s N O
2s
AO of N AO of O
2s
MO of NO
 The MO diagram
: for CO

• Generate an MO Diagram for CO

• What is the bond order?
• What is the HOMO?
• What is the LUMO?
• Draw a corresponding Lewis dot structure
• Bonus: Based on your answers above, what can you envision
for the bonding interaction of CO with a transition metal (like
Fe)?
The MO diagram for CO

Bond order for CO = (10-4)/2 = 1 + 1  + 1  = 3