Kimia Anorganik

Teknik Kimia Universitas Diponegoro

Theories of Covalent Bonding

(Chapter 11)

Teguh Riyanto, M.T.

@teguh_ryt
teguh_ryt@che.undip.ac.id
Outline

VALENCE BOND (VB) THEORY

AND ORBITAL HYBRIDIZATION

MODES OF ORBITAL OVERLAP

AND THE TYPES OF COVALENT BONDS

MOLECULAR ORBITAL (MO) THEORY

AND ELECTRON DELOCALIZATION
VALENCE BOND (VB) THEORY
AND ORBITAL HYBRIDIZATION
The Central Themes of VB Theory
The basic principle of VB theory is that a covalent bond forms when
orbitals of two atoms overlap and a pair of electrons occupy the
overlap region.
The central themes of VB theory derive from this principle:
1. Opposing spins of the electron pair. As the exclusion principle
requires, the space formed by the overlapping orbitals has a
maximum capacity for two electrons that have opposite spins.
2. Maximum overlap of bonding orbitals. The greater the orbital
overlap, the closer the nuclei are to the electrons, and the
stronger the bond. Extent of overlap depends on orbital shape
and direction. p or d orbital involved in a bond is oriented so as to
maximize overlap.
3. Hybridization of atomic orbitals.

Methane = CH2?? ➔ CH4

Linus Pauling proposed that, during bonding, the valence orbitals

in the isolated atoms become new orbitals in the molecule.
Quantum-mechanical calculations show that if we mathematically “mix” certain combinations of
orbitals, we form new ones whose spatial orientations do match the observed molecular shapes.
The process of orbital mixing is called hybridization, and the new atomic orbitals are called hybrid
orbitals.
The Central Themes of VB Theory

4. Features of hybrid orbitals.

→ The number of hybrid orbitals formed equals the number of atomic orbitals
mixed.
→ The type of hybrid orbitals formed varies with the types of atomic orbitals mixed.
→ The shape and orientation of a hybrid orbital maximize its overlap with the
orbital of the other atom in the bond.

It is useful to think of hybridization as a process in which atomic orbitals mix,

hybrid orbitals form, they overlap other orbitals, and electrons enter the overlap region
with opposing spins, thus forming stable bonds.
In truth, hybridization is a mathematical concept that helps us explain the molecular
shapes we observe.
Types of Hybrid Orbitals

We postulate the type of hybrid orbitals in a molecule after we observe its shape.
1. sp Hybridization
When two electron groups surround the central atom, we observe a linear shape, as in
BeCl2.

??
no unpaired electrons, Be cannot form bonds. Be atom can promote an electron from
the 2s orbital to an empty 2p orbital, resulting in two unpaired electrons that could
participate in two bonds with Cl atoms to form BeCl2.
However, this would result in two nonidentical bonds: the 2s orbital of Be would overlap
with a 3p orbital of one Cl atom to form one bond, while the 2p orbital of Be would
overlap with a 3p orbital of a second Cl atom to form the second bond. But
experimentally, we know that the two Be−Cl bonds are identical in length and energy.
Types of Hybrid Orbitals
Types of Hybrid Orbitals

2. sp2 Hybridization 4. sp3d Hybridization

3. sp3 Hybridization 5. sp3d2 Hybridization

Types of Hybrid Orbitals
MODES OF ORBITAL OVERLAP
AND THE TYPES OF COVALENT
BONDS
Orbital Overlap in Single and Multiple Bonds
Orbitals can overlap by two modes—end to end or side to side—which gives rise to two
types of covalent bonds—sigma and pi.
1. End-to-End Overlap and Sigma (σ) Bonding.
→ A sigma bond is formed by end-to-end overlap of orbitals.
→ A sigma bond has its highest electron density along the bond axis and is shaped like
an ellipse rotated about its long axis (like a football).
→ All single bonds are σ bonds.

Example: Ethane (C2H6)

end-to-end overlap
Orbital Overlap in Single and Multiple Bonds
2. Side-to-Side Overlap and Pi (π)
Bonding.
→ A pi bond is formed by side to side
overlap of orbitals.
→ A pi bond has two regions (lobes)
of electron density, one above and
one below the σ-bond axis. The
two electrons in one π bond
occupy both lobes.
→ A double bond consists of one σ
bond and one π bond, which
increases electron density
between the nuclei.
→ A triple bond consists of one σ
bond and two π bonds.

Example: Ethylene (C2H4) and

Acetylene (C2H2)
Orbital Overlap in Single and Multiple Bonds

Because orbitals overlap less side to side than they do end to end, a π bond is
weaker than a σ bond; thus, for carbon-carbon bonds, a double bond is less than
twice as strong as a single bond. The electron density between the nuclei increases
from single to double to triple bond.

~347 kJ/mol ~614 kJ/mol ~839 kJ/mol

Orbital Overlap and Rotation Within a Molecule

The type of overlap—end to end or side to side—affects

rotation around the bond:
1. Sigma (σ) bond.
A σ bond allows free rotation because the extent of
overlap is not affected. If you could hold one CH3
group of ethane, the other CH3 could spin without
affecting the overlap of the C−C σ bond.

2. Pi (π) bond.
A π bond restricts rotation because p orbitals must be
parallel to each other to overlap most effectively.
Holding one CH2 group in ethylene and trying to spin
the other decreases the side-to-side overlap and
breaks the π bond. For this reason, distinct cis and
trans structures exist for compounds such as 1,2-
dichloroethylene.
MOLECULAR ORBITAL (MO) THEORY
AND ELECTRON DELOCALIZATION
Molecular Orbital (MO) Theory
Molecular Orbital (MO) theory can be applied to explain magnetic
and spectral properties of molecules that cannot be explained by
VSEPR and VB theories. The MO model is a quantum-mechanical
treatment for molecules similar to the one for atoms: just as an
atom has atomic orbitals (AOs) of given energies and shapes that
are occupied by the atom’s electrons, a molecule has molecular
orbitals (MOs) of given energies and shapes that are occupied by
the molecule’s electrons.

There is a key distinction between VB and MO theories:

→ VB theory pictures a molecule as a group of atoms bonded
through overlapping of valence-shell atomic and/or hybrid
orbitals occupied by localized electrons.
→ MO theory pictures a molecule as a collection of nuclei with
orbitals that extend over the whole molecule and are occupied
by delocalized electrons.

Despite its usefulness, MO theory has the drawback that MOs are
more difficult to visualize than the shapes of VSEPR theory or the
hybrid AOs of VB theory.
Formation of Molecular Orbitals

Bonding Antibonding
Shape and Energy of H2 Molecular Orbitals
1. Bonding MO
A bonding MO is lower in energy than the AOs that form it. The electron density is
spread mostly between the nuclei, nuclear repulsions decrease while nucleus-
electron attractions increase. Moreover, two electrons in this MO can delocalize
their charges over a larger volume than they could in nearby, separate AOs, which
lowers electron repulsions.
2. Antibonding MO
An antibonding MO is higher in energy than the AOs that form it. Most of the
electron density outside the internuclear region and a node between the nuclei,
nuclear repulsions increase.

Both the bonding and

antibonding MOs of H2 are
sigma (σ) MOs because
they are cylindrically
symmetrical about an
imaginary line between
the nuclei.
Electrons in Molecular Orbitals
1. Filling MOs with electrons.
• MOs are filled in order of increasing energy (Aufbau principle)
• An MO can hold a maximum of two electrons with opposite spins (Exclusion principle)
• Orbitals of equal energy are half-filled, with electron spins parallel, before any of them are
filled (Hund’s rule)
2. MO energy-level diagrams. An MO diagram shows the relative energy and number of electrons
for each MO.
3. Electron configuration. The symbol of each occupied MO is written in parentheses, with the
number of electrons in it as a superscript outside.
C = 1s2 2s2 2p2
H2 = (σ1s)2
Electrons in Molecular Orbitals
4. Bond order

Bond order =
1
2
( ) (
no. of e − in bonding MOs − no. of e − in antibonding MOs 
 )
• Bond order > 0: the molecule is more stable than the separate atoms, so it will form.
• Bond order = 0: the molecule is as stable as the separate atoms, so it will not form.
• In general, the higher the bond order, the stronger the bond is.

 2 − 0
1
Bond order H 2 =
2
Bond order H 2 = 1

we can predict the existence

of molecules
Do He2+ and He2 Exist?
Electrons configuration:
He = 1s2

Electron configuration: 𝝈𝟏𝒔 𝟐 𝝈∗𝟏𝒔 𝟐 Electron configuration: 𝝈𝟏𝒔 𝟐 𝝈∗𝟏𝒔 𝟏

Bond order: 0 Bond order: 1/2

He2 does not exist. He2+ has a relatively weak bond,
but it should exist.
Homonuclear Diatomic
Molecules of Period 2 Elements
Homonuclear diatomic molecules are composed of two identical atoms. In addition to
H2 from Period 1, you’re familiar with N2, O2, and F2 from Period 2 as the elemental
forms under standard conditions. Others in Period 2—Li2, Be2, B2, C2, and Ne2—are
observed, if at all, at high temperatures.

s-block p-block
Bonding in the s-Block
Homonuclear Diatomic Molecules
Li and Be atoms have electrons in inner (1s) and outer (2s) AOs, but we ignore the inner
ones because, in general, only outer (valence) AOs interact enough to form MOs.
Electrons configuration: Electrons configuration:
Li = 1s2 2s1 Be = 1s2 2s2

𝟐
Valence electron configuration: 𝝈𝟐𝒔 Valence electron configuration:
Bond order: 1 𝝈𝟐𝒔 𝟐 𝝈∗𝟐𝒔 𝟐
Li2 has been observed. Bond order: o
Be2 has never been observed.
Shape and Energy of MOs
from Atomic p-Orbital Combinations
• There are three different p orbitals, px, py, and pz.
• p orbitals can overlap by two modes, which correspond to two ways their wave
functions combine.
→ End-to-end combination gives a pair of sigma (σ) MOs, 𝝈𝟐𝒑 and 𝝈∗𝟐𝒑
→ Side-to-side combination gives a pair of pi (π) MOs, 𝝅𝟐𝒑 and 𝝅∗𝟐𝒑
• Bonding MOs have most of electron density between the nuclei, and antibonding MOs
have most of it outside the internuclear region with a node between the nuclei.
Shape and Energy of MOs
from Atomic p-Orbital Combinations
• The order of energy levels for MOs, whether
bonding or antibonding, is based on the order of
AO energy levels and on the mode of p-orbital
overlap
→ MOs formed from 2s orbitals are lower in
energy than MOs formed from 2p orbitals
→ Bonding MOs are lower in energy than
antibonding MOs: 𝝈𝟐𝒑 is lower in energy than
𝝈∗𝟐𝒑 and 𝝅𝟐𝒑 is lower than 𝝅∗𝟐𝒑
→ Atomic p orbitals overlap more extensively
end to end than side to side. Thus, the 𝝈𝟐𝒑 MO
is usually lower in energy than the 𝝅𝟐𝒑 MO.
The destabilizing effect of the 𝝈∗𝟐𝒑 MO is
greater than that of the 𝝅∗𝟐𝒑 MO.

The energy order for MOs derived from 2s and 2p

orbitals:
𝝈𝟐𝒔 < 𝝈∗𝟐𝒔 < 𝝈𝟐𝒑 < 𝝅𝟐𝒑 < 𝝅∗𝟐𝒑 < 𝝈∗𝟐𝒑
Shape and Energy of MOs
from Atomic p-Orbital Combinations
Recall that only AOs of similar energy interact
enough to form MOs.
This fact leads to two energy orders:
1. Without mixing of s and p orbitals: O2, F2, and Ne2.
Lying at the right of Period 2, O, F, and Ne are
relatively small. Thus, as electrons start to pair up
in the half-filled 2p orbitals, strong repulsions
raise the energy of the 2p orbitals high enough
above the 2s orbitals to prevent orbital mixing.

The energy order of the MOs derived from 2s and

2p orbitals for O2, F2, and Ne2 :
𝝈𝟐𝒔 < 𝝈∗𝟐𝒔 < 𝝈𝟐𝒑 < 𝝅𝟐𝒑 < 𝝅∗𝟐𝒑 < 𝝈∗𝟐𝒑
Shape and Energy of MOs
from Atomic p-Orbital Combinations
2. With mixing of s and p orbitals: B2, C2, and N2.
B, C, and N atoms are relatively large, with 2p AOs
only half-filled, so repulsions are weaker. As a
result, orbital energies are close enough for some
mixing to occur between the 2s of one atom and
the end-on 2p of the other. The effect is to lower
the energy of the 𝝈𝟐𝒔 and 𝝈∗𝟐𝒔 MOs and raise the
energy of the 𝝈𝟐𝒑 and 𝝈∗𝟐𝒑 MOs; the π MOs are
not affected.

The energy order of the MOs derived from 2s and

2p orbitals for B2, C2, and N2 :
𝝈𝟐𝒔 < 𝝈∗𝟐𝒔 < 𝝅𝟐𝒑 < 𝝈𝟐𝒑 < 𝝅∗𝟐𝒑 < 𝝈∗𝟐𝒑
Homonuclear Diatomic Molecules of
Period 2 Elements
• Higher bond order
correlates with greater
bond energy and shorter
bond length.
• Orbital occupancy
correlates with magnetic
properties. If a substance
has unpaired electrons, it
is paramagnetic, and if all
electrons are paired, the
substance is diamagnetic.
Heteronuclear Diatomic Molecules:
HF and NO
Heteronuclear diatomic molecules have asymmetric MO diagrams because the AOs of the
different atoms have unequal energies. Atoms with greater effective nuclear charge (Zeff)
pull their electrons closer, so they have more stable (lower energy) AOs and higher EN
values.
1. Bonding in HF
F has high Zeff, the 1s, 2s, and 2p orbitals
have lower energy than the 1s of H. The
half-filled 2p orbital of F interacts with the
1s of H through end-on overlap, which
forms σ and σ* MOs. The two filled 2p
orbitals of F are called nonbonding MOs.
They are not involved in bonding, they
have the same energy as the isolated AOs.
The F 2p orbital contributes more to the HF
bond than the H 1s does. In polar covalent
molecules, bonding MOs are closer in
energy to the AOs of the more
electronegative atom.
Heteronuclear Diatomic Molecules:
HF and NO
2.Bonding in NO

Both structures show a double bond, but the

measured bond energy suggests a bond order
higher than 2. It is not clear where the lone
electron resides. The lone electron occupies
one of the 𝝅∗𝟐𝒑 orbitals.

more in keeping
Bond order NO = 8 − 3
1
2 with the data than
Bond order NO = 2.5 either Lewis structure

The 2p orbitals of N contribute more to the

orbital that holds the lone electron, so it
spends more time closer to N.
Two Polyatomic Molecules:
Benzene and Ozone
The orbital shapes and MO diagrams for polyatomic molecules are too complex.
The model eliminates the need for resonance forms. We cannot draw one Lewis structure
for either benzene or ozone. The VB model also uses resonance because it relies on
localized bonds. In contrast, MO theory pictures a structure of delocalized σ and π MOs.
Lewis structure Molecular orbitals
Ozone, O3
O O O
O O O O O O

Benzene, C6H6
H H
HC CH
H C H H C H
C C C C
HC CH
C C C C
H C H H C H
HC CH
H H