Chapter 9
Molecular Geometry
and Bonding Theories
Dr V Paideya
2025
© 2015 Pearson Education
Molecular Shapes
• Lewis Structures show bonding and lone pairs, but
do not denote shape.
• However, we use Lewis Structures to help us
determine shapes.
• Here we see some common shapes for molecules
with two or three atoms connected to a central atom.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
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.
• This is the Valence-Shell Electron-Pair Molecular
Geometries
and Bonding
Repulsion (VSEPR) model. Theories
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Electron Domains
• In general, each
nonbonding pair, single
bond, or multiple bond
produces an electron
domain around the
central atom. Because
electron domains are
negatively charged, they
repel one another. The
central atom in this
molecule, A, has four
electron domains. Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Valence-Shell Electron-Pair
Repulsion (VSEPR) Model
“The best arrangement of
a given number of
electron domains is the
one that minimizes the
repulsions among them.”
(The balloon analogy in
the figure to the left
demonstrates the
maximum distances,
which minimize Molecular
repulsions.) Geometries
and Bonding
Theories
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Electron-Domain Geometries
• Table shows the
electron-domain
geometries for two
through six electron
domains around a
central atom.
• To determine the
electron-domain
geometry, count the
total number of lone
pairs, single, double,
and triple bonds on Molecular
Geometries
the central atom. and Bonding
Theories
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Terminology
Basic VSEPR Formula:
AXyEz
(Count regions of electron density)
Where: A – central atom
X – terminal atom
E – lone pairs on the central atom
Molecular
Molecule adopts the shape that minimises the electron
Geometries
pair repulsion and Bonding
7
Theories
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Molecular Geometries
• Once you have determined the electron-domain
geometry, use the arrangement of the bonded atoms
to determine the molecular geometry.
• Tables 9.2 and 9.3 show the potential molecular
geometries. We will look at each electron domain Molecular
to see what molecular geometries are possible. Geometries
and Bonding
Theories
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Linear Electron Domain
• In the linear domain, there is only one
molecular geometry: linear.
• NB: 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
Theories
© 2015 Pearson Education, Inc.
Trigonal Planar Electron Domain
• There are two molecular geometries:
– trigonal planar, if all electron domains are
bonding, and
– bent, if one of the domains is a Molecular
Geometries
nonbonding pair. and Bonding
Theories
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Examples of VSEPR Formulae
4 electron domains 4 electron domains 4 electron domains
Electron Domain Electron Domain Electron Domain
Geometry - Tetrahedral Geometry - Tetrahedral Geometry - Tetrahedral
Molecular Geometry Molecular Geometry Molecular Geometry
AX4 AX3E AX2E2
Tetrahedral Trigonal pyramidal Angular/bent
Bond angle 109.5o Bond angle 107o Bond angle 104.5o
No LPs 1LP - repulsion between 2BPs & 2LPs– repulsion
Angles between Hs LP and BPs between LPs greater
maximum Angle between Hs than repulsion between
Molecular
Geometries
decrease LP and BPand Bonding
BP- Bonding pair LP- Lone pair Theories
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Determining the Geometry of a
Molecule
To apply VSEPR theory:
1. Draw a plausible Lewis structure
2. Determine the number of e- pairs, & write a formula
(AXyEz)
3. Determine the Electron Domain Geometry (Table)
4. Determine the Molecular geometry (Table)
Molecular
Geometries
and Bonding
12
Theories
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Tetrahedral Electron Domain
• There are three molecular geometries:
– tetrahedral, if all are bonding pairs,
– trigonal pyramidal, if one is a nonbonding
pair, and Molecular
Geometries
– bent, if there are two nonbonding pairs. and Bonding
Theories
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Nonbonding Pairs and Bond Angle
• Nonbonding pairs are physically
larger than bonding pairs.
• Therefore, their repulsions are
greater; this tends to compress
bond angles.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Multiple Bonds and Bond Angles
• Double and triple
bonds have larger
electron domains
than single bonds.
• They exert a greater
repulsive force than
single bonds, making
their bond angles
greater. Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Expanding beyond the Octet Rule
• Remember that some elements can
break the octet rule and make more
than four bonds (or have more than four
electron domains).
• The result is two more possible electron
domains: five = trigonal bipyramidal;
six = octahedral (as was seen in the
slide on electron-domain geometries).
Molecular
Geometries
and Bonding
Theories
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Molecules with Expanded Valence Shells
• A central atom
from period 3 can
have more than
an octet
• 5 electron
domains adopt a
Trigonal-
bipyramidal Molecular
geometry Geometries
and Bonding
Theories
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Electron Domain: Trigonal Bipyramidal
• Lower-energy conformations result from having
nonbonding electron pairs in equatorial, rather Molecular
than axial, positions in this geometry. Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Trigonal bipyramidal: 4 distinct molecular geometries
(PCl5) Trigonal
bipyramidal
(SF4) Seesaw
(ClF3) T -
Shaped
Molecular
(XeF2) Linear
Geometries
and Bonding
Theories
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Octahedral domain: 3 distinct molecular geometries
(SF6)
Octahedral
(BrF5)
Square
pyramidal
(XeF4)
Square planar
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Molecular Geometry (learn!)
Molecular
Geometries
and Bonding
21
21 Theories
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Example
Question:
Predict the molecular geometry of the polyatomic
anion, ICl4−.
Cl
Cl I Cl
Cl
EDG - 6 electron domains, sp3d2 hybridized –
Octahedral
MG – AX4E2 – Square planar
Molecular
Geometries
and Bonding
22
Theories
© 2015 Pearson Education, Inc.
Example
Question: Predict the molecular geometry of PF5 and
SF6
F F F
F F
P S
F F F F
F F
EDG - 5 electron domains, sp3d hybridized – Trigonal
bipyramidal
MG – AX5 – Trigonal bipyramidal
EDG - 6 electron domains, sp3d2 hybridized – Octahedral
Molecular
MG – AX6 – Octahedral Geometries
and Bonding
23
Theories
© 2015 Pearson Education, Inc.
Structures with Multiple Covalent
Bonds
Treat double and triple bonds as single bonds.
E.g. CO2
O C O
EDG - 2 electron domains, sp hybridized – Linear
MG – AX2 – Linear
Question: Predict the molecular geometry of SO2
(draw all Lewis structures)
Expanded octet
EDG - 3 electron domains, sp2 hybridized – Trigonal planar
MG – AX2E – Angular or bent
Resonance structures Molecular
Geometries
EDG - 3 electron domains, sp2 hybridized – Trigonal planar
and Bonding
24
Theories
– Pearson
MG© 2015 E – Angular
AX2Education, Inc. or bent
Structures with More than One
Central Atom
Determine the molecular geometry around each
central atom in H2SO4
Derive the VSEPR formula for Oxygen (1&2) & sulfur:
O1&2: AX2E2 S: AX4
Look up the molecular geometry from the table:
Molecular
O1&2: angular/bent S: tetrahedral
Geometries
and Bonding
25
Theories
© 2015 Pearson Education, Inc.
Shapes of Larger Molecules
In larger molecules, it
makes more sense to talk
about the geometry of a
particular atom rather than
the geometry of the
molecule as a whole.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Practice
Predict electron-domain & molecular
geometries for following:
SiCl4, H3O+, SF4, SnCl4, XeF4, CH3OH,
[PCl6]-, XeOF4;
NH2CH2COOH
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Comparison of the
Polarity of Two Molecules
A NONPOLAR molecule A POLAR molecule
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Polar Molecules
A molecule will be polar ONLY if it
contains polar bonds AND the molecule is
NOT symmetrical
Symmetric molecules
Molecular
Linear Trigonal planar Tetrahedral Trigonal Octahedral
Geometries
bipyramidal29 and Bonding
Theories
© 2015 Pearson Education, Inc.
Molecular Shapes and Dipole
Moments
Dipole moment, μ, describes the degree of
polarity of a molecule
E.g. 1: HCl
δ+ H – Cl δ-
Polar bond polar molecule
E.g. 2: CO2
O=C=O
Why is CO2 not polar even thou the CO bonds are polar?
CO bonds are polar and equal in strength BUT in Geometries
Molecular
opposite direction, .: cancel each other out and Bonding
30
© 2015 Pearson Education, Inc. NONPOLAR MOLECULE
Theories
Molecular Shapes and Dipole
Moments
E.g. 3: H2O δ-
Each OH is polar
O Non-symmetric molecule
AX2E2
H H polar molecule
δ+ δ+
E.g. 5: CH3F
E.g. 4: CCl4
Cl Different
F Atom here
C Cl
Cl Cl C H
H H
Altho each CCl bond is polar
AX4 Symmetrical molecule, Unequal polar bonds,Molecular
CCl cancel each other out Geometries
.: NOT symmetrical and Bonding
nonpolar molecule polar molecule 31
Theories
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Molecular Shapes and Dipole
Moments
F B +ve H electronegativity
B +ve 2.1
F -ve H +ve 2.0
B B F -ve 4.0
F F F F
BF bonds are polar BF and BH bonds are polar
AX3 - symmetrical AX3 but different atoms
BF3 molecule is Non- symmetrical
Non-POLAR HBF2 molecule
Molecular
POLAR Geometries
and Bonding
32
Theories
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Bond Order & Bond Length
Bond Order – describes the multiplicity of a covalent
bond. The higher the bond order, the more electrons
there are in the bond, the stronger the bond.
Bond Length – the distance between the nuclei of two
atoms bonded with a covalent bond
Multiplicity of Bond Bond Bond
Bond Order Strength Length
Single 1 Weakest Longest
Double 2
Triple 3 Strongest Shortest
Molecular
Geometries
and Bonding
33
Theories
© 2015 Pearson Education, Inc.
Bond Order & Bond Length
triple, BO=3 CH2CHCN
H H 1s&2p Acrylonitrile
H C C C N
double, BO=2
Single, BO=1 1s&1p
1s
BOND STRENGTH (kJ/mol) LENGTH (pm)
C—C 347 154
C=C 611 134
CC 837 121
The GREATER the number of bonds (bond order)Molecular
Geometries
the HIGHER the bond strength and the SHORTER and
the
Bonding
34
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bond. Theories
Valence-Bond Theory
• VSEPR great for shapes but not so
good for explaining why bonds
exist
• Using quantum mechanics (atomic
orbitals!) a simple model that looks
at orbital overlap provides a picture
of chemical bonding (valence-
bond-theory)
• Covalent bonds form when
electrons are shared by adjacent
atoms
• Sharing can only occur when
orbitals on the two atoms overlap.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Hybrid Orbitals
• To explain geometries, we often
assume that the atomic orbitals of an
atom mix to form new orbitals called
hybrid orbitals.
• The process of mixing orbitals as
atoms approach each other is called
hybridisation.
• Hybrid orbitals – determined by the Molecular
Geometries
Electron Domain Geometry and Bonding
Theories
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sp Hybrid Orbitals
Consider beryllium: Be
– In its ground electronic state, it
would not be able to form
bonds because it has no
singly-occupied 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 Bonding
Theories
© 2015 Pearson Education, Inc.
sp 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 Bonding
Theories
© 2015 Pearson Education, Inc.
sp 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 Bonding
Theories
© 2015 Pearson Education, Inc.
sp2 Hybrid Orbitals
Using a similar model for boron (B) leads to sp2
hybridisation, i.e.
• Mixing a specific number of orbitals results in the
same number of hybrid orbitals
• The 3 hybrid orbitals in BF3 come from mixing a 2s
Molecular
and two of the 2p Geometries
and Bonding
Theories
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sp2 Hybrid Orbitals (BF3 Cont…)
• 3 degenerate sp2 orbitals.
• All lie in the same plane
• 120° apart – BF3 is trigonal planar
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
sp3 Hybrid Orbitals
With carbon we get sp3 hybridisation, i.e.
…
…four degenerate sp3 orbitals.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Show H2O has sp3 hybridisation…
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Hybridisation involving d orbitals
For geometries involving expanded octets
on the central atom (e.g. PF5), we must
use d orbitals in our hybrids.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Steps to predict hybrid orbitals
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Hybrid Orbital
Summary
➢ Once the electron-
domain geometry is
known, the hybridization
state of the atom is
known.
➢ Number of hybrid orbitals
equals the sum of the
individual orbitals
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Multiple Bonds
s (sigma)- overlap
of two orbitals along
the internuclear axis.
p (pi) - sideways overlap
of two p orbitals.
H – H ; has one s bond
O = O ; has one s bond and a p bond
N ≡ N ; has one s bond and two p bond
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Bonding in Molecules
• Single bonds are
always σ-bonds.
• Multiple bonds
have one σ-bond,
all other bonds
are π-bonds.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.
Localized or Delocalized Electrons
• Bonding electrons (σ or π) that are
specifically shared between two atoms
are called localized electrons.
• In many molecules, we can’t describe
all electrons that way (resonance); the
other electrons (shared by multiple
atoms) are called delocalized
electrons.
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc.