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Theories of Covalent Bonding

11.1 Valence Shell Electron Pair Repulsion Theory

11.2 Valence Bond (VB) Theory and Orbital Hybridization

11.3 Molecular Orbital (MO)Theory and Electron Delocalization

11-1
 Covalent Bonding and
Orbital Overlap
• Lewis structures and VSEPR do not explain why a bond
forms. How do we account for shape in terms of quantum
mechanics?
• What are the orbitals that are involved in bonding?
• We use Valence Bond Theory:
• Bonds form when orbitals on atoms overlap.
• A covalent bond forms when the orbitals of two atoms
overlap and the overlap region, which is between the nuclei,
is occupied by a pair of electrons.
• There are two electrons of opposite spin in the orbital overlap.
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 Covalent Bonding and
Orbital Overlap

Hydrogen, H2

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Hydrogen fluoride, HF

Fluorine, F2

11-4
 Covalent Bonding and
Orbital Overlap
• As two nuclei approach each other their atomic orbitals
overlap.
• As the amount of overlap increases, the energy of the
interaction decreases.
• At some distance the minimum energy is reached.
• The minimum energy corresponds to the bonding
distance (or bond length).
• As the two atoms get closer, their nuclei begin to repel
and the energy increases.
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 Covalent Bonding and
Orbital Overlap
• At the bonding distance, the attractive forces between
nuclei and electrons just balance the repulsive forces
(nucleus-nucleus, electron-electron).

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 Hybrid Orbitals

• Atomic orbitals can mix or hybridize in order to adopt an

appropriate geometry for bonding.
• Hybridization is determined by the electron domain
geometry.
sp Hybrid Orbitals
• Consider the BeF2 molecule (experimentally known to
exist):

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 Hybrid Orbitals
sp Hybrid Orbitals
• Be has a 1s22s2 electron configuration.
• There is no unpaired electron available for bonding.
• We conclude that the atomic orbitals are not adequate to
describe orbitals in molecules.
• We know that the F-Be-F bond angle is 180 (VSEPR
theory).
• We also know that one electron from Be is shared with
each one of the unpaired electrons from F.

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 Hybrid Orbitals
sp Hybrid Orbitals
• We assume that the Be orbitals in the Be-F bond are 180
apart.
• We could promote and electron from the 2s orbital on Be to the
2p orbital to get two unpaired electrons for bonding.
• BUT the geometry is still not explained.
• We can solve the problem by allowing the 2s and one 2p
orbital on Be to mix or form a hybrid orbital.
• The hybrid orbital comes from an s and a p orbital and is
called an sp hybrid orbital.
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 Hybrid Orbitals
sp Hybrid Orbitals
• The lobes of sp hybrid orbitals are 180º apart.
• Since only one of the Be 2p orbitals has been used in
hybridization, there are two unhybridized p orbitals
remaining on Be.

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Figure 11.2 The sp hybrid orbitals in gaseous BeCl2.

atomic
orbitals

hybrid
orbitals

orbital box diagrams

11-13
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Figure 11.2 The sp hybrid orbitals in gaseous BeCl2(continued).

orbital box diagrams with orbital contours

11-14
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Figure 11.3 The sp2 hybrid orbitals in BF3.

11-16
 sp2 and sp3
Hybrid Orbitals
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Figure 11.4 The sp3 hybrid orbitals in CH4.

11-18
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Figure 11.5 The sp3 hybrid orbitals in NH3.

11-19
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Figure 11.5 continued The sp3 hybrid orbitals in H2O.

11-20
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Figure 11.6 The sp3d hybrid orbitals in PCl5.

11-21
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Figure 11.7 The sp3d2 hybrid orbitals in SF6.

11-22
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Hybrid Orbitals

Key Points

The number of hybrid orbitals obtained equals the number of

atomic orbitals mixed.
The type of hybrid orbitals obtained varies with the types of
atomic orbitals mixed.

Types of Hybrid Orbitals

sp sp2 sp3 sp3d sp3d2

11-23
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11-24
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Figure 11.8
The conceptual steps from molecular formula to the hybrid orbitals
used in bonding.

Step 1 Step 2 Step 3

Molecular shape
Molecular Lewis and e- group Hybrid
formula structure arrangement orbitals

11-25
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SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

PROBLEM: Use partial orbital diagrams to describe mixing of the atomic

orbitals of the central atom leads to hybrid orbitals in each of
the following:
(a) Methanol, CH3OH (b) Sulfur tetrafluoride, SF4

PLAN: Use the Lewis structures to ascertain the arrangement of

groups and shape of each molecule. Postulate the hybrid
orbitals. Use partial orbital box diagrams to indicate the hybrid
for the central atoms.

SOLUTION: (a) CH3OH H The groups around C are

C arranged as a tetrahedron.
H O
H H
O also has a tetrahedral
arrangement with 2 nonbonding
e- pairs.

11-26
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SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

continued

2p 3 2p 3
sp sp

hybridized hybridized
2s single C atom 2s single O atom
C atom O atom

(b) SF4 has a seesaw shape with 4 bonding and 1 nonbonding e- pairs.
F
F S
F 3d 3d
F

3p
3
sp d
hybridized
S atom
3s S atom
11-27
 Hybrid Orbitals
Hybridization Involving d Orbitals
• Since there are only three p-orbitals, trigonal bipyramidal
and octahedral electron domain geometries must involve
d-orbitals.
• Trigonal bipyramidal electron domain geometries require
sp3d hybridization.
• Octahedral electron domain geometries require sp3d2
hybridization.
• Note the electron domain geometry from VSEPR theory
determines the hybridization.
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 Hybrid Orbitals
Summary
1. Draw the Lewis structure.
2. Determine the electron domain geometry with VSEPR.
3. Specify the hybrid orbitals required for the electron pairs
based on the electron domain geometry.

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 Multiple Bonds

-Bonds: electron density lies on the axis between the

nuclei.
• All single bonds are -bonds.
-Bonds: electron density lies above and below the plane
of the nuclei.
• A double bond consists of one -bond and one -bond.
• A triple bond has one -bond and two -bonds.
• Often, the p-orbitals involved in -bonding come from
unhybridized orbitals.
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Multiple Bonds
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Figure 11.9 The bonds in ethane(C2H6).

both C are sp3 hybridized

s-sp3 overlaps to bonds

sp3-sp3 overlap to form a bond

relatively even
distribution of electron
density over all
bonds

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 Multiple Bonds

Ethylene, C2H4, has:

• one - and one -bond;
• both C atoms sp2 hybridized;
• both C atoms with trigonal planar electron pair and molecular
geometries.

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Figure 11.10 The and bonds in ethylene (C2H4).

overlap in one position -

p overlap -

electron density

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 Multiple Bonds

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 Multiple Bonds

• When triple bonds form (e.g. N2) one -bond is always

above and below and the other is in front and behind the
plane of the nuclei.

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 Multiple Bonds

Consider acetylene, C2H2

• the electron pair geometry of each C is linear;
• therefore, the C atoms are sp hybridized;
• the sp hybrid orbitals form the C-C and C-H -bonds;
• there are two unhybridized p-orbitals;
• both unhybridized p-orbitals form the two -bonds;
• one -bond is above and below the plane of the nuclei;
• one -bond is in front and behind the plane of the nuclei.

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Figure 11.11 The and bonds in acetylene (C2H2).

overlap in one position -

p overlap -

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 Multiple Bonds

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 Multiple Bonds

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 Multiple Bonds
Delocalized Bonding
• So far all the bonds we have encountered are localized
between two nuclei.
• In the case of benzene
• there are 6 C-C bonds, 6 C-H bonds,
• each C atom is sp2 hybridized,
• and there are 6 unhybridized p orbitals on each C
atom.

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 Multiple Bonds
Delocalized Bonding

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 Multiple Bonds
Delocalized Bonding
• In benzene there are two options for the 3 bonds
• localized between C atoms or
• delocalized over the entire ring (i.e. the electrons
are shared by all 6 C atoms).
• Experimentally, all C-C bonds are the same length in
benzene.
• Therefore, all C-C bonds are of the same type (recall
single bonds are longer than double bonds).
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 Multiple Bonds
General Conclusions
• Every two atoms share at least 2 electrons.
• Two electrons between atoms on the same axis as the
nuclei are bonds.
-Bonds are always localized.
• If two atoms share more than one pair of electrons, the
second and third pair form -bonds.
• When resonance structures are possible, delocalization is
also possible.
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 Molecular Orbitals

• Some aspects of bonding are not explained by Lewis

structures, VSEPR theory and hybridization. (E.g. why
does O2 interact with a magnetic field?; Why are some
molecules colored?)
• For these molecules, we use Molecular Orbital (MO)
Theory.
• Just as electrons in atoms are found in atomic orbitals,
electrons in molecules are found in molecular orbitals.

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SAMPLE PROBLEM 11.2 Describing the Bond in Molecules

PROBLEM: Describe the types of bonds and orbitals in acetone, (CH3)2CO.

PLAN: Use the Lewis structures to ascertain the arrangement of groups and
shape at each central atom. Postulate the hybrid orbitals taking note of
the multiple bonds and their orbital overlaps.

SOLUTION: sp
2
sp
2

sp3 hybridized
O
2
O
O sp
H H
sp3 hybridized H C H sp 2
sp
3
C C 3
H H sp 2 2
H H sp C sp C sp
3
C
C H
sp2 hybridized 3 sp
3 H 3C CH3
3 sp 3 H
sp H sp
H sp 3

bond
bonds
11-49
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The Central Themes of MO Theory

A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular orbitals.

Atomic wave functions are summed to obtain molecular wave

functions.

If wave functions reinforce each other, a bonding MO is formed

(region of high electron density exists between the nuclei).

If wave functions cancel each other, an antibonding MO is formed

(a node of zero electron density occurs between the nuclei).

11-50
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Figure 11.14
An analogy between light waves and atomic wave functions.

Amplitudes of wave
functions added

Amplitudes of
wave functions
subtracted.

11-51
 Molecular Orbitals

• Molecular orbitals:
• each contain a maximum of two electrons;
• have definite energies;
• can be visualized with contour diagrams;
• are associated with an entire molecule.
The Hydrogen Molecule
• When two AOs overlap, two MOs form.

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 Molecular Orbitals
The Hydrogen Molecule
• Therefore, 1s (H) + 1s (H) must result in two MOs for
H2:
• one has electron density between nuclei (bonding
MO);
• one has little electron density between nuclei
(antibonding MO).
• MOs resulting from s orbitals are MOs.
(bonding) MO is lower energy than * (antibonding)
MO.
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 Molecular Orbitals
The Hydrogen Molecule

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 Molecular Orbitals
The Hydrogen Molecule
• Energy level diagram or MO diagram shows the energies
and electrons in an orbital.
• The total number of electrons in all atoms are placed in
the MOs starting from lowest energy ( 1s) and ending
when you run out of electrons.
• Note that electrons in MOs have opposite spins.
• H2 has two bonding electrons.
• He2 has two bonding electrons and two antibonding
electrons.
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 Figure 11.15 The MO diagram for H2.

Filling molecular orbitals with electrons follows the

same concept as filling atomic orbitals.

*1s
Energy

1s 1s

H2 bond order
= 1/2(2-0) = 1
1s

AO MO AO
of H of H2 of H

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 Second-Row Diatomic
Molecules
Electron Configurations and Molecular
Properties
• Two types of magnetic behavior:
• paramagnetism (unpaired electrons in molecule): strong
attraction between magnetic field and molecule;
• diamagnetism (no unpaired electrons in molecule): weak
repulsion between magnetic field and molecule.
• Magnetic behavior is detected by determining the mass
of a sample in the presence and absence of magnetic
field:
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