Chemistry, The Central Science, 10th edition

Theodore L. Brown, H. Eugene LeMay, Jr., and Bruce E. Bursten

Chapter 9
Molecular Geometries
and Bonding Theories

John D. Bookstaver
Molecular
St. Charles Community College Geometries
St. Peters, MO and Bonding
What Determines the Shape of a Molecule?
• Electron pairs, whether they be
bonding or nonbonding, repel
each other.
• By assuming the electron pairs
are placed as far as possible from
each other, we can predict the
shape of the molecule.

Molecular
Geometries
and Bonding
There are five
fundamental geometries
for molecular shape

Molecular
Geometries
and Bonding
 Molecular
Geometries
and Bonding
 Electron Domains
• We can refer to the electron pairs as
electron domains.
• Each pair of electrons count as an electron
domain, whether they are in a lone pair, in
a single, double or triple bond.
• This molecule has four electron domains.
 Those ABE forms are used to ease the understanding of molecular shapes.
A: represents the central atom.
B: represents the bonding atoms (or bonding electron pairs or number of bonds regardless of
their nature, single, double or triple).
E: represents the number of nonbonding electron pairs.
CH4 (Methane) AB4 NH3 (Ammonia) AB3E H2O (Water) AB2E2 Molecular
Geometries
and Bonding
 Electron-Domain Geometries
• All one must do is count the
number of electron domains in
the Lewis structure.
• The geometry will be that
which corresponds to that
number of electron domains.
 In order to predict molecular shape, we assume the valence electrons
repel each other. Therefore, the molecule adopts whichever 3D
geometry minimizes this repulsion.
• We call this process Valence Shell Electron Pair Repulsion (VSEPR)
Molecular
theory. Geometries
and Bonding
• Electron domain geometry: When considering the geometry about the
central atom, we consider all electrons (lone pairs and bonding pairs).

• When naming the molecular geometry, we focus only on the positions

of the atoms.

Molecular
Geometries
and Bonding
 VSEPR Model
• To determine the shape of a molecule, we distinguish between
lone pairs (or non-bonding pairs, those not in a bond) of electrons
and bonding pairs (those found between two atoms).

• We define the electron domain geometry (or orbital geometry) by

the positions in 3D space of ALL electron pairs (bonding or non-
bonding).

• The electrons adopt an arrangement in space to minimize e--e-

repulsion.

Molecular
Geometries
and Bonding
 Molecular
Geometries
and Bonding
• Examples – Draw the Lewis structures, and then determine
the orbital geometry of each:
e- domain ABE e- domain Molecular
form geometry geometry (shape)
1. H2S 4 AB2E2 Tetrahedral Bent
2. CO2 2 AB2 Linear Linear
3. PCl3 4 AB3E Tetrahedral Trigonal pyramidal
4. CH4 4 AB4 Tetrahedral Tetrahedral
5. SO2 3 AB2E Trigonal planar Bent
Molecular
Geometries
and Bonding
• To determine the electron pair ( electron domain) geometry:
 draw the Lewis structure,
 count the total number of electron pairs around the central atom,
 arrange the electron pairs in one of the above geometries to
minimize e--e- repulsion, and count multiple bonds as one bonding
pair.
 But then we have to account for the shape of the molecule.

Molecular
Geometries
and Bonding
 Molecular Geometries
Within each electron domain,
then, there might be more than
one molecular geometry.

Molecular
Geometries
and Bonding
 Linear Electron Domain

• In this domain, there is only one molecular geometry: linear.

• NOTE: If there are only two atoms in the molecule, the
molecule will be linear no matter what the electron domain is.

Molecular
Geometries
and Bonding
 Nonbonding Pairs and Bond Angle
• Nonbonding pairs are physically larger
than bonding pairs.
• Therefore, their repulsions are
greater; this tends to decrease bond
angles in a molecule.

Molecular
Geometries
and Bonding
• By experiment, the H-X-H bond angle decreases on moving from C to N to O:
H

H C H H N H O
H H H H
109.5O 107O 104.5O
• Since electrons in a bond are attracted by two nuclei, they do not repel as
much as lone pairs.
• Therefore, the bond angle decreases as the number of lone pairs increase.

• Similarly, electrons in multiple bonds repel more than electrons in single

bonds.
Cl
111.4o C O
Molecular
Cl 124.3o
Geometries
and Bonding
Multiple Bonds and Bond Angles

• Double and triple bonds place greater

electron density on one side of the central
atom than do single bonds.
• Therefore, they also affect bond angles.

Molecular
Geometries
and Bonding
 Trigonal Planar Electron Domain

• There are two molecular geometries:

 Trigonal planar, if all the electron domains are bonding Molecular
 Bent, if one of the domains is a nonbonding pair. Geometries
and Bonding
 Tetrahedral Electron Domain

• There are three molecular geometries:

 Tetrahedral, if all are bonding pairs
 Trigonal pyramidal if one is a nonbonding pair Molecular
Geometries

 Bent if there are two nonbonding pairs and Bonding

 Molecular
Geometries
and Bonding
Examples – Determine the molecular geometry of each,
including shapes and bond angles:
Shape Angles

1. H2S Bent <109.5°

2. CO2 Linear 180°
3. PCl3 Trigonal pyramid <109.5°
4. CH4 Tetrahedral 109.5°
5. SO2 Bent <120°
Molecular
Geometries
and Bonding
Trigonal Bipyramidal Electron Domain

• There are two distinct

positions in this geometry:
 Axial
 Equatorial

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
Trigonal Bipyramidal Electron Domain

Lower-energy conformations result from having nonbonding

electron pairs in equatorial, rather than axial, positions in this
geometry.
Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Trigonal Bipyramidal Electron Domain
• There are four
distinct molecular
geometries in this
domain:
 Trigonal bipyramidal
 Seesaw
 T-shaped
 Linear

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
Octahedral Electron Domain
• All positions are
equivalent in the
octahedral domain.
• There are three
molecular
geometries:
 Octahedral
 Square pyramidal
 Square planar

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Larger Molecules
In larger molecules,
it makes more
sense to talk about
the geometry about
a particular atom
rather than the
geometry of the
molecule as a
whole.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
Larger Molecules
This approach makes
sense, especially because
larger molecules tend to
react at a particular site in
the molecule.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Molecular Shape and Molecular Polarity
• When there is a difference in electronegativity between two
atoms, then the bond between them is polar.

• It is possible for a molecule to contain polar bonds, but not be polar.

• For example, the bond dipoles in CO2 cancel each other because
CO2 is linear.

Molecular
Geometries
and Bonding
 Molecular
Geometries
and Bonding
• In water, the molecule is not linear and the bond dipoles do not
cancel each other.
• Therefore, water is a polar molecule.

• The overall polarity of a molecule depends on its molecular geometry.

Molecular
Geometries
and Bonding
Polarity
By adding the individual bond
dipoles, one can determine
the overall dipole moment for
the molecule.

Molecular
Geometries
and Bonding
Polarity

Molecular
Geometries
and Bonding
 Polar

Polar Polar
Polar Nonpolar

Molecular
Geometries
and Bonding
 Opposite direction cancel Net dipole

Net dipole = 0 BF3 = No net dipole moment

Molecular
Geometries
and Bonding
 Overlap and Bonding

• We think of covalent bonds forming through the sharing of

electrons by adjacent atoms.
• In such an approach this can only occur when orbitals on the
two atoms overlap.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Overlap and Bonding
• Increased overlap brings
the electrons and nuclei
closer together while
simultaneously
decreasing electron-
electron repulsion.
• However, if atoms get too
close, the internuclear
repulsion greatly raises
the energy. Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

But it’s hard to imagine tetrahedral, trigonal bipyramidal, and

other geometries arising from the atomic orbitals we
recognize.
Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

• Consider beryllium:
 In its ground electronic
state, it would not be
able to form bonds
because it has no
singly-occupied orbitals.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

But if it absorbs the

small amount of
energy needed to
promote an electron
from the 2s to the 2p
orbital, it can form two
bonds.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals
• Mixing the s and p orbitals yields two degenerate
orbitals that are hybrids of the two orbitals.
 These sp hybrid orbitals have two lobes like a p orbital.
 One of the lobes is larger and more rounded as is the s
orbital.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals
• These two degenerate orbitals would align
themselves 180 from each other.
• This is consistent with the observed geometry of
beryllium compounds: linear.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

• With hybrid orbitals the orbital diagram for beryllium would

look like this.
• The sp orbitals are higher in energy than the 1s orbital but
lower than the 2p. Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

Using a similar model for boron leads to…

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

…three degenerate sp2 orbitals.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

With carbon we get…

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

…four degenerate
sp3 orbitals.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 Hybrid Orbitals

For geometries involving expanded octets on the central

atom, we must use d orbitals in our hybrids.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
Hybrid Orbitals

This leads to five degenerate

sp3d orbitals…

…or six degenerate sp3d2

orbitals.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
Hybrid Orbitals

Once you know the

electron-domain
geometry, you know
the hybridization
state of the atom.

Molecular
Geometries
and
© 2009, Prentice-Hall, Bonding
Inc.
 To remember
• For trigonal Planar molecular shape if the 3 surrounding
atoms are the same the molecule is non polar molecule
because the dipoles cancel each other.
• For tetrahedral: if the 4 surrounding atoms are the same
the molecule is non-polar. This is important for carbon
compounds with 4 single bonds.

Molecular
Geometries
and Bonding
 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.
• When resonance structures are possible, delocalization is also
possible.

• If two atoms share more than one pair of electrons, the second and
third pair form -bonds.
Molecular
Geometries
and Bonding
Examples – Draw Lewis Structures (including resonance).
Determine the total number of σ and π bonds in the molecule,
and the bond order of each bond:
O O 2σ and 1π
1. O3 O O O O
Each bond 1.5
O O
O

2. SO3 O
S
O S
S
O O
O O

3σ and 1π each bond 1.33

3. CO2 O C O Molecular
Geometries
2σ and 2π each bond 2 and Bonding