Unit 9 - Molecular

Geometry
 Molecular Shape
Chemical/Physical Properties Related to
Molecular Shape
Lewis Structures
Show atoms and bonds, but not spatial
orientations (3-D)
Molecular Models
Show orientations and bond angles; help us
understand physico-chemical properties

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Lewis Structures vs Models

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 Molecular Shape
Bond Angle:
Angle defined
by covalent bonds
between three adjacent
atoms
Molecular Geometry:
Shape defined
by lowest energy
3-D arrangement OCO angle HOH angle
of atoms
= 180⁰ (linear) = 104.5⁰ (bent)
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 Valence-Shell Electron-Pair Repulsion Theory
(VSEPR)
VSEPR Theory:
• Geometric arrangement of electron pairs around
atoms based on minimizing repulsion energy
Electron Pair Geometry:
• Spatial arrangement of bonding e− pairs and lone pairs
(non-bonding) of valence electrons
Molecular Geometry:
• Defined by relative arrangement of atoms (bonding
pairs) in molecule
• Bond angles depend on e− pair repulsion
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 Predicting a VSEPR Structure
1. Draw the Lewis structure
2. Determine the steric number (SN)
of the central atom
SN = (number of atoms bonded to central atom)
+ (number of lone pairs on central atom)
3. Use the SN to determine the geometry
around the central atom
4. Optimize molecular structure by determining the
number of lone pairs and bonding pairs of
electrons

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 Electron Pair Repulsions
Electron Pair Repulsion Order:
• Lone pair—Lone pair = greatest repulsion
• Lone pair—Bonding pair is next
• Bonding pair—Bonding pair = least repulsion
• Double bonds exert more repulsion than single bonds

Bond angles around central atom decrease as

repulsive forces increase

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 Geometric Forms: SN = 2
Electron Pair Geometry Molecular Geometry
Linear Linear

Examples: CO2, BeF2, HCN, C2H2

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 Geometric Forms: SN = 3
Electron Pair Geometry Molecular Geometry
Trigonal Planar If 3 bonding, 0 non-bonding
Trigonal Planar

BF3

If 2 bonding, 1 non-bonding
Bent

NO2-

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 Geometric Forms: SN = 4
Electron Pair Geometry Molecular Geometry
Tetrahedral If 4 bonding, 0 non-bonding
Tetrahedral

If 3 bonding, 1 non-bonding
Trigonal Pyramidal

If 2 bonding, 2 non-bonding
Bent

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 Molecular Geometry: SN = 4

Tetrahedral Trigonal pyramid Bent

Note: Bond angles decrease as

number of lone pairs increases
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 Geometric Forms: SN = 5
Electron Pair Geometry Molecular Geometry
Trigonal Bipyramidal If 5 bonding, 0 non-bonding
Trigonal Bipyramidal

If 4 bonding, 1 non-bonding
Seesaw

If 3 bonding, 2 non-bonding
T-Shaped

If 2 bonding, 3 non-bonding
Linear

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 Molecular Geometry: SN = 5
Seesaw

SF4
T-Shaped

ClF3
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 Geometric Forms: SN = 6
Electron Pair Geometry Molecular Geometry
Octahedral If 6 bonding, 0 non-bonding
Octahedral
If 5 bonding, 1 non-bonding
Square Pyramidal

If 4 bonding, 2 non-bonding
Square Planar
If 3 bonding, 3 non-bonding
T-Shaped
If 2 bonding, 4 non-bonding
Linear
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 Molecular Geometry: SN = 6
Square Pyramidal

IF5
Square Planar

XeF4
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Atoms Lone Steric
Electron Geometry Molecular geometry
Bonded Pairs Number
6 0 6 Octahedral Octahedral
5 1 6 Octahedral Square pyramidal
4 2 6 Octahedral Square planar
5 0 5 Trig. Bipyramidal Trig. Bipyramidal
4 1 5 Trig. Bipyramidal See-saw
3 2 5 Trig. Bipyramidal T-shaped
4 0 4 Tetrahedral Tetrahedral
3 1 4 Tetrahedral Trig. Pyramidal
2 2 4 Tetrahedral Bent
3 0 3 Trig. Planar Trig. Planar
2 1 3 Trig. Planar Bent
2 0 2 Linear Linear
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 Practice: Molecular Geometry

Determine the molecular geometry of:

a) SeCl4 b) PSCl3 c) SiF5─

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 Dipole Moment and Molecular Geometry
The dipole moment is a measure of the degree of charge
separation in a molecule
Measurements are based on the fact that polar molecules
are oriented by an electric field. This orientation affects
the capacitance of the charged plates that create the
electric field.

Requirements for Polar Molecule:

1. Molecule must contain polar bonds (i.e., covalent
bond between atoms with ΔEN)
2. Orientation of polar bonds results in charge
separation from one part of the molecule to another
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 Example: CO vs. CO2

Polar but linear shape results in partial

Polar bond… no other bond
to cancel; polar!
bonds… charges canceling out; nonpolar!

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 Polar Bonds and Polar Molecules

Bond Dipole:
• Separation of
charge within a
covalent bond

Polar Molecule:
• Have nonzero
dipole moments
• Vectors of bond
dipoles sum > zero
Polar!
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 Dipole Moment and Molecular Geometry
Dipole moment arrow with + on partial
plus side (or least electronegative atom)
Geometry example: CO2 is linear, and
H2O is bent.
+
+ + + O +
O C O
H H
The vectors add to zero (cancel) For H2O, a net vector points up
for CO2 Water has a dipole moment
Its dipole moment is zero = polar
= nonpolar
Note: Any geometry with polar bonds and any
asymmetry in the arrangement of electron pairs
would have a nonzero dipole moment. These
molecules are considered polar. 9 | 21
Dipole Moment and Molecular Geometry
Polar molecules experience attractive forces between molecules; in response,
they orient themselves in a d+ to d- manner.
Attraction between molecules impacts molecular properties
Example: The attractive forces due to the polarity lead the molecule to have a
higher boiling point.
Example: Molecular polarity affects solubility in water.
We can see this illustrated with two compounds:

There is no net polarity; this The net polarity is up; this is a

is a nonpolar molecule polar molecule

Boiling point 48°C 9 | 22 Boiling point 60°C

 Problem to consider
Which of the following molecules would be expected to
have a zero dipole moment?

a. GeF4

b. SF2

c. XeF2

d. H2O

e. AsF3 9 | 23
 Measuring Polarity
Dipole moment (μ): Measured value defining extent of
separation of + and − charge centers in a molecule
(Units = debyes (D); 1 D = 3.34 × 10−30 coul∙m )
Structure with Dipole Moment
Formula
Bond Dipole(s) (debyes)

HF 1.91

H2O 1.85

NH3 1.47

CHCl3 1.04

CCl3F 0.45
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 Atomic Orbitals and Bonds
Bond electron density holding two atoms together.
Atomic Orbitals / Tetrahedral Geometry:
• Requires overlap of four orbitals of the central
atom with orbitals of outer atoms
• Available orbitals (one s + three p) not oriented to
yield 109° bond angles observed in tetrahedral
geometry!
• Need new theory to explain orientation
of bonds in molecules
Valence Bond Theory (Linus Pauling)
Bond = overlap between 2 atomic or hybrid orbitals
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 Valence-Bond Theory
Assumes that covalent bonds form when
orbitals on different atoms overlap
Hybridization: mixing of atomic orbitals
to generate new sets of orbitals that form
covalent bonds with other atoms
Hybrid atomic orbital: one of a set of equivalent
orbitals created when specific atomic orbitals
are mixed

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 Hybrid orbitals
Hybrid orbitals are named by using the atomic orbitals that
combined:
• one s orbital + one p orbital gives two sp orbitals
• one s orbital + two p orbitals gives three sp2 orbitals
• one s orbital + three p orbitals gives four sp3 orbitals
• one s orbital + three p orbitals + one d orbital gives five sp3d orbitals
• one s orbital + three p orbitals + two d orbitals gives six sp3d2 orbitals
Hybrid orbitals have definite directional characteristics, as described
below
Hybrid Orbitals Geometric Arrangement Number of Orbitals Example
sp Linear 2 Be in BeF2
sp2 Triognal Planar 3 B in BF3
sp3 Tetrahedral 4 C in CH4
sp3d Trigonal bipyramidal 5 P in PCl5
sp3d2 Octahedral 6 S in SF6
 Orbital Overlap: Sigma Bonds
Sigma (σ) bond: covalent bond having highest
electron density between the two atoms along
the bond axis

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 Hybrid orbitals
First, the paired 2s electron is promoted (excited) to the
unfilled orbital. Now each orbital has one electron.
Second, these orbitals are hybridized, giving four sp3
hybrid orbitals.

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 Tetrahedral: sp3 Hybrid Orbitals
Tetrahedral orientation of bonding orbitals
results from “hybridization” of the s and p
orbitals

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Other sp3 Hybrid Examples

Note:
Lone pairs
(non-
bonding)

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 Trigonal Planar: sp2 Hybridization
Mixing of one s and two p orbitals:

Unhybridized orbitals used to form double bonds

(“pi” bond) 9 | 32
 Trigonal Planar: sp2 Hybridization

pi (π) bond:
electron density is concentrated above/below the
bonding axis

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 Linear: sp Hybridization
Mixing of one s and one p orbital:
Unhybridized orbitals
used to form triple
bond (= one σ and
two π bonds)

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 Carbon Dioxide: Multiple π Bonds
Carbon: sp hybridized
• sp orbitals = σ bonds
• unhybridized orbitals = π bonds

Oxygen: sp2 hybridized

• one sp2 orbital = σ bond
• two sp2 orbitals = lone pairs
• unhybridized orbital = π bond

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 Octahedral: sp3d2 Hybridization
Formed by mixing one s, two d, and three p
orbitals. All six hybridized orbitals used to form
sigma bonds

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Trigonal Bipyramid: sp3d Hybridization
Formed by mixing one s, one d, and three p
orbitals - all five hybrid orbitals used to form
sigma bonds

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 Hybrid orbitals
To obtain the bonding description about any atom
in a molecule:

1. Write the Lewis electron-dot formula.

2. Use VSEPR to determine the electron arrangement
about the atom.
3. From the arrangement, deduce the hybrid orbitals.
4. Assign the valence electrons to the hybrid orbitals
one at a time, pairing only when necessary.
5. Form bonds by overlapping singly occupied hybrid
orbitals with singly occupied orbitals of another atom.
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 Summary of Hybridization
Orientation of Number of σ Molecular Angles between
Hybridization
Hybrid Orbitals Bonds Geometries Hybrid Orbitals

sp 2 Linear 180˚

3 Trigonal planar
sp2 2 Bent
120˚

4 Tetrahedral
sp3 3 Trigonal pyramidal 109.5˚
2 Bent

5 Trigonal bipyramidal
4 Seesaw 90˚ (ax to eq)
sp3d 3 T-shaped 180˚ (eq to eq)
2 Linear

6 Octahedral
5 Square pyramidal
sp3d2 4 Square planar 90˚
3 T-shaped
2 Linear
 A Problem to consider
Describe the bonding in XeF4 using hybrid orbitals
From the Lewis formula for a molecule, determine its
geometry about the central atom using the VSEPR model.

The Lewis formula of XeF4 is

The xenon atom has four single bonds and two lone pairs. It will
require six orbitals to describe the bonding.
From this geometry, determine the hybrid orbitals on this atom,
assigning its valence electrons to these orbitals one at a time.
This suggests that you use sp3d2 hybrid orbitals on xenon
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 A Problem to consider
Each Xe-F bond is formed by the overlap of a xenon sp3d2
hybrid orbital with a singly occupied fluorine 2p orbital.
Xe atom Xe atom
(ground state) (in XeF4)

5d 5d

5p sp3d2

hybridization
5s lone pairs Xe-F bonds

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 Description of Multiple Bonds

One hybrid orbital is required for each bond

(whether a single or a multiple bond) and for
each lone pair.

Multiple bonding involves the overlap of one

hybrid orbital and one (for a double bond) or
two (for a triple bond) nonhybridized p orbitals.

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 Description of Multiple Bonds
To describe a multiple bond, we need to distinguish
between two kinds of bonds.
• A σ (sigma) bond is a “head-to-head” overlap of
orbitals with a cylindrical shape about the bond axis.
This occurs when two “s” orbitals overlap or “p”
orbitals overlap along their axis.

• A π (pi) bond is a “side-to-side” overlap of parallel

“p” orbitals, creating an electron distribution above
and below the bond axis.

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9 | 44
 Multiple Bonding - Ethene
Two of the sp2 hybrid orbitals of each carbon overlap with the
1s orbitals of the hydrogens.
The remaining sp2 hybrid orbital on each carbon overlap to form
a sigma bond.
The remaining “unhybridized” 2p orbitals on each of the carbon
atoms overlap side-to-side forming a pi bond.

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 sp2 Hybrid Orbitals

Hybrid orbitals overlap to

form a σ bond.

Unhybridized p orbitals
overlap to form a π bond.

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sp Hybrid Orbitals

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 Bond Rotation
Because the orbitals that form the s bond point along
the internuclear axis, rotation around that bond does not
require breaking the interaction between the orbitals

But the orbitals that form the p bond interact above and
below the internuclear axis, so rotation around the axis
requires the breaking of the interaction between the
orbitals

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Bond Rotation

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 Bond Rotation
The description of a p bond helps to explain the cis-
trans isomers of 1,2-dichloroethene.

The overlap of the parallel p orbitals restricts the

rotation around the C=C bond. This fixes the geometric
positions of Cl: either on the same side (cis) or on
different sides (trans) of the C=C bond.
H H H Cl

C C C C

Cl Cl Cl H
cis trans
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 Problems with Bonding Theories

Lewis structures /valence bond theory:

• Modeled bonding capacities of elements,
but did not account for molecular shapes.
VSEPR + valence bond theories:
• Account for observed molecular geometries, but
not magnetic properties.
• For example, O2 is attracted to a magnetic field
(paramagnetic) while N2 is repelled slightly
(diamagnetic).
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 Molecular Orbital (MO) Theory

The wave functions of atomic orbitals in atoms are

combined to create molecular orbitals (MOs) in
molecules.

The number of molecular orbitals formed is equal

to the number of atomic orbitals combined.

Molecular orbitals spread out over entire molecule

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 Types of Molecular Orbitals
Bonding orbitals:
• Hold atoms together by increasing electron density
between nuclear centers in molecules.
• Are lower in energy (more stable) than atomic orbitals
from which they are formed.
Antibonding orbitals:
• Destabilize the molecule because they do not increase
electron density between nuclear centers.
• Are higher in energy (less stable) than atomic orbitals from
which they are formed.

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 Molecular Orbital Theory
MO Diagram:
• Energy level diagram for molecular orbitals; shows
formation of bonding / antibonding orbitals.
Sigma (σ) Bond:
• Covalent bond with the highest electron density
along the bond axis.
pi (π) Bond:
• Formed by mixing of atomic orbitals not oriented
along the bonding axis in a molecule.
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 MO Guidelines
1. The total number of MO formed equals the number
of atomic orbitals used in the mixing process.
2. Orbitals with similar energy and shape mix more
effectively than do those that are different.
3. Orbitals of different principal quantum numbers have
different sizes and energies, resulting in less effective
mixing.
4. A MO can accommodate two electrons with opposite
spin.
5. Electrons are placed in MO diagrams according
to Hund’s rule.
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 Molecular Orbital Theory: H2
The two 1s orbitals may be added or subtracted
to yield two sigma MOs (1 bonding/1 antibonding)
σ1s*
(Anti-bonding)

σ1s
Isolated (Bonding) Isolated
H atom H atom

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 Molecular Orbital Diagram: H2
Atomic Molecular Atomic
Orbital Orbital σ1s*
Orbital
(Anti-bonding)

Isolated σ1s Isolated

H atom (Bonding)
H atom

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 Bond Order and Stability
Bond Order = ½*(# of bonding e- - # antibonding e-)
H2 H 2- He2

Bond Order: Bond Order: Bond Order:

½*(2 – 0) = 1 ½*(2 – 1) = 1/2 ½*(2 – 2) = 0

Stable Stable Not Stable

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 Molecular Orbital Diagram: p orbitals
For O2, F2, and Ne2 For B2, C2, and N2

p orbitals can overlap:

• head-to-head, gives two σ molecular interactions between the 2s and 2p atomic
orbitals orbitals are strong enough to switch the
• side-by-side overlap gives four π molecular orbital energy of the σ2p and π2p
molecular orbitals

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MO Scheme for N2
Electron configuration for N2:
σ2s2σ2s*2σ2p2π2p4

Bond order
½*(8 − 2) = 3

N2 has three bonds

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 MO Scheme for O2
Electron configuration for O2:
σ2s2σ2s*2σ2p2π2p4 π2p*2

Bond order = ½*(8 − 4) = 2

O2 has two bonds

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Paramagnetism and Diamagnetism
Paramagnetism:
Atoms or molecules having unpaired electrons are
attracted to magnetic fields.
• Example: O2
Diamagnetism:
Atoms or molecules having all paired electrons are
repelled by magnetic fields.
• Example: N2
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 MO Diagrams for N2 and O2

N2 has no unpaired electrons O2 has two unpaired electrons in π2p*

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Diamagnetic Paramagnetic
 Other Diatomic Molecules

MO Theory predicts both magnetic properties and

stability of diatomic molecules
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 Theoretical Bond Orders and Experimental Data for
Second-Period Homonuclear Diatomic Molecules

Bond Bond Length Bond Dissociation Magnetic

Molecule
Order (pm) Energy (kJ/mol) Character
Li2 1 267 110 Diamagnetic
Be2 0 * * *
B2 1 159 290 Paramagnetic
C2 2 124 602 Diamagnetic
N2 3 110 942 Diamagnetic
O2 2 121 494 Paramagnetic
F2 1 142 155 Diamagnetic
Ne2 0 * * *

* means that no stable molecule has been observed

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 MO for Heteroatomic Molecules

Effective nuclear charge alters

the diagram; atomic orbitals
for O are lower in energy.

The odd electron is more likely

to be found on N since it is in
an orbital closer in energy to
the atomic orbitals of the
nitrogen atom.
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 MO Theory: Summary
Advantages:
• Provides the most complete picture of covalent
bonding, including bond types
and bond orders
• Accounts for magnetic properties
Disadvantage:
• The most difficult to apply to large molecules;
does not account for molecular shape

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 Hydrogen Bonding
Hydrogen Bond: Special class of dipole-dipole
interactions due to strength

One polar molecule is attracted to H- from another

polar molecular that is covalently bonded to strongly
electronegative atom (N, O, or F)
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 Hydrogen Bonding in DNA
H-bonding in complementary nucleotide bases

9 | 69
 Learning Objectives
● Describe the formation of covalent bonds in terms of atomic overlap
● Apply valence bond theory in terms of hybrid and unhybridized atomic orbitals
● Determine the hybrid orbitals in a species based on the molecular geometry
● Distinguish between σ bonds and π bonds and be able to determine the number of
each in a molecule
● Describe multiple bonds in terms of atomic overlap
● Explain the concept of resonance in terms of π bonding
● Describe molecular orbital configurations and apply molecular orbital theory to
determine magnetic behavior and bond order/stability
● Describe bonding vs antibonding orbitals
● Calculate bond order based on molecular orbital diagrams

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