Chapter 5

Molecular Geometry
and Hybridization
of Atomic Orbitals
Molecular Geometry
• Molecular geometry is the three-dimensional arrangement of

atoms in a molecule.
• A molecule’s geometry affects its physical and chemical
properties, such as melting point, boiling point, density, and
the types of reactions it undergoes.
• Basis of this approach is the assumption that electron pairs in
the valence shell of an atom repel one another.
• The geometry that the molecule ultimately assumes minimizes
the repulsion.
This approach to the study of molecular geometry is called the
valence-shell electron-pair repulsion (VSEPR) model,

It accounts for the geometric arrangements of electron pairs around
a central atom in terms of the electrostatic repulsion between
electron pairs.
Predicting the geometry of molecules (and ions) will be convenient

if divide molecules into two categories, according to whether or not
the central atom has lone pairs.
Molecules in Which the Central Atom Has No Lone Pairs
Will consider molecules that contain atoms of only two elements,
A and B,
A is the central atom.
These molecules have the general formula ABx,
where x is an integer 2, 3, . . . .
let us take a close look at the geometry of molecules with

the formulas AB2, AB3, AB4, AB5, and AB6.
AB2: Beryllium Chloride (BeCl2)
Lewis structure “ball-and-stick”
Bonding pairs repel each other, they must be at opposite ends of a

straight line in order for them to be as far apart as possible
Thus, the Cl-Be-Cl angle is predicted to be 180° and the molecule

is linear
AB3: Boron Trifluoride (BF3)
Contains three covalent bonds
Geometry of BF3 is trigonal planar because the

three end atoms are at the corners of an equilateral
triangle, which is planar:
Thus, each of the three F-B-F angles

is 120°, and all four atoms lie in the
same plane.
AB4: Methane (CH4)
Geometry of CH4 is tetrahedral
The bond angles are all 109.5°
Geometry of PCl5 is trigonal

AB5: Phosphorus Pentachloride (PCl5) bipyramid
The angle between any two
equatorial bonds is 120°;
that between an axial bond
and an equatorial bond is
90°, and that between the
two axial bonds is 180°.
AB6: Sulfur Hexafluoride (SF6)
The most stable arrangement of the six SF bonding pairs is in the

shape of an octahedron
All bond angles are 90° except the one made by the bonds
between the central atom and the pairs of atoms that are
diametrically opposite each other. That angle is 180°.
Molecules in Which the Central Atom Has One or
More Lone Pairs
There are three types of repulsive forces, according to the
VSEPR model, the repulsive forces decrease in the following
order:
To keep track, designate a molecules with lone pairs as ABxEy,

where A is the central atom
B is a surrounding atom
E is a lone pair on A.
Both x and y are integers; x 2, 3, . . . , and y 1, 2, . . . .
AB2E: Sulfur Dioxide (SO2)
Lewis structure
SO2 molecule consist of three electron pairs on the central S atom.

(two are bonding pairs and one is a lone pair)
The overall arrangement of three electron pairs is trigonal planar.
But because one of the electron pairs is a lone pair, the SO2
molecule has a “bent” shape.
lone-pair versus bonding-pair repulsion is greater than
the bonding-pair versus bonding-pair repulsion, so the
OSO angle is less than 120°
AB3E: Ammonia (NH3)
Arrangement of four electron pairs is tetrahedral
In NH3 one of the electron pairs is a lone pair, so the geometry of

NH3 is trigonal pyramidal
Because the lone pair repels the bonding pairs more
strongly, the three NH bonding pairs are pushed
closer together:
Thus, the HNH angle in ammonia is smaller than the ideal

tetrahedral angle of 109.5°
AB2E2: Water (H2O)
A water molecule contains two bonding pairs

and two lone pairs
The overall arrangement of the four electron pairs in water

is tetrahedral
two lone pairs on the central O atom. These lone pairs tend
to be as far from each other as possible. Consequently,
the two OOH bonding pairs are pushed toward each other,
and the HOH angle is 104.5°. The geometry of H2O is bent:
Guidelines for Applying the VSEPR Model
1. Write the Lewis structure of the molecule, considering only the

electron pairs around the central atom
2. Count the number of electron pairs around the central atom (bonding
pairs and lone pairs). Treat double and triple bonds as though they were
single bonds. Predict the overall arrangement of the electron pairs and
the geometry of the molecule using the tables
In predicting bond angles, repulsion between lone pairs and bonding

pair should be taken into account, general there is no easy way to
predict bond angles accurately
Dipole Moments
hydrogen fluoride is a covalent compound with a polar bond.
There is a shift of electron density from H to F because the F

atom is more electronegative than the H atom
The consequent charge separation can be represented as

A quantitative measure of the polarity of a bond is its dipole moment
(µ), which is the product of the charge Q and the distance r between
the charges:
Dipole moments are usually expressed in debye units (D), named

for Peter Debye.
• Diatomic molecules containing atoms of different elements (CO,
and NO) have dipole moments and are called polar molecules.
• Diatomic molecules containing atoms of the same element ( H2,

O2, and F2) are examples of nonpolar molecules because they do
not have dipole moments
• For a molecule made up of three or more atoms both the polarity

of the bonds and the molecular geometry determine whether
there is a dipole moment.
Even if polar bonds are present, the molecule will not necessarily
have a dipole moment.
Carbon dioxide (CO2),
The arrows show the shift of electron density from the less
electronegative carbon atom to the more electronegative
oxygen atom.
The two bond moments in CO2 are equal in magnitude. Because

they point in opposite directions in a linear CO2 molecule, the sum
or resultant dipole moment would be zero
Consider the NH3 and NF3 molecules
In both cases, the central N atom has a lone pair, whose charge
density is away from the N atom
Consider the NH3 and NF3 molecules
• N is more electronegative than H, and F is more electronegative
than N.
• The shift of electron density in NH3 is toward N and so
contributes a larger dipole moment.
• The NF bond moments are directed away from the N atom and so
together they offset the contribution of the lone pair to the dipole
moment.
• Thus, the resultant dipole moment in NH3 is larger than that in
NF3.

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Chapter 5

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Molecular Geometry

• Molecular geometry is the three-dimensional arrangement of

valence-shell electron-pair repulsion (VSEPR) model,

Predicting the geometry of molecules (and ions) will be convenient

let us take a close look at the geometry of molecules with

Lewis structure “ball-and-stick”

Bonding pairs repel each other, they must be at opposite ends of a

Thus, the Cl-Be-Cl angle is predicted to be 180° and the molecule

Contains three covalent bonds

Geometry of BF3 is trigonal planar because the

Thus, each of the three F-B-F angles

Geometry of PCl5 is trigonal

The most stable arrangement of the six SF bonding pairs is in the

To keep track, designate a molecules with lone pairs as ABxEy,

SO2 molecule consist of three electron pairs on the central S atom.

Arrangement of four electron pairs is tetrahedral

In NH3 one of the electron pairs is a lone pair, so the geometry of

Thus, the HNH angle in ammonia is smaller than the ideal

A water molecule contains two bonding pairs

The overall arrangement of the four electron pairs in water

1. Write the Lewis structure of the molecule, considering only the

In predicting bond angles, repulsion between lone pairs and bonding

There is a shift of electron density from H to F because the F

The consequent charge separation can be represented as

Dipole moments are usually expressed in debye units (D), named

• Diatomic molecules containing atoms of the same element ( H2,

• For a molecule made up of three or more atoms both the polarity

The two bond moments in CO2 are equal in magnitude. Because

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