The molecular geometry, or the

shape of a molecule is described

by the geometric figure formed
when the atomic nuclei are
imagined to be joined in
straight lines.

EOS
2

Ideal molecular geometry is based on the idea that

pairs of valence electrons in bonded atoms repel
one another
An electron group is any collection of valence
electrons, localized in a region around a central
atom, that repels other groups of valence electrons
The mutual repulsions among electron groups lead
to an orientation of the groups that is called
electron-group geometry
EOS
3

How can electrons on the central atom be

arranged so they are as far apart as possible?
2 electron groups linear
3 electron groups trigonal
planar
4 electron groups tetrahedral
5 electron groups trigonal
bipyramidal
6 electron groups octahedral
EOS
4

In the VSEPR notation used

to describe molecular
geometries, the central atom
in a structure is denoted as A,
terminal atoms as X, and the
lone pairs of electrons as E
EOS
5

The optimal repulsion arrangement is opposite ends

of a line
Geometry is unaffected by lone pairs of electrons
EOS
6

The optimal repulsion arrangement is the corners of

a trianglenote the planarity
7

With a lone pair, the geometry is essentially the same

EOS

The optimal repulsion arrangement is the corners of

a regular tetrahedronfour equal triangular faces
There can be one or two lone pairs on the central
atom
EOS
9

EOS

10

The optimal repulsion arrangement is a triangle with

a bisecting line through the triangle face
Up to three lone pairs can be included here

EOS
11

EOS
12

13

The optimal repulsion arrangement is at the face

centers of a cube
One or two lone-pair geometries are most common
EOS
14

Illustration

EOS
15

Valence Bond (VB) Theory states that a covalent bond

is formed by the pairing of two electrons with opposing
spins in the region of overlap of atomic orbitals
between two atoms
This overlap region has a high
electron charge density
The more extensive the overlap
between two orbitals, the stronger is
the bond between two atoms
EOS
16

EOS
17

Most of the electrons in a molecule remain in the same

orbital locations that they occupied in the separated
atoms
Bonding electrons are localized in the region of atomic
orbital overlap
For orbitals with directional lobes, maximum overlap
occurs when atomic orbitals overlap end to end; that
is, a hypothetical line joining the nuclei of the bonded
atoms passes through the region of maximum overlap
EOS
18

Based on ground-state electron configuration,

carbon should have only two bonds
If a 2s electron is promoted to
an empty 2p orbital, then four
unpaired electrons can give
rise to four bonds
These four orbitals become
mixed, or hybridized to form
bonds
HybridizationVideo

EOS
19

Occurs most often for central atom only

The total number of hybrid orbitals is equal
to the number of atomic orbitals combined

Hybrid orbitals may overlap with pure atomic

orbitals or with other hybrid orbitals

EOS
20

The carbon atom in

methane (CH4) has
bonds that are sp3
hybrids
Note that in this
molecule carbon
has all single
bonds
EOS
21

Ammonia (NH3)
is similar except
the lone pair of
electrons
occupies the 4th
hybrid orbital

EOS
22

This hybridization scheme is useful in describing

double covalent bonds
Comprised of one 2s orbital and two 2p orbitals to
produce a set of three sp2 hybrid orbitals

The empty 2p orbital

remains unhybridized
EOS
23

The geometric distribution of the three sp2 hybrid

orbitals is within a plane, directed at 120o angles
This distribution gives a trigonal planar
molecular geometry, as predicted by VSEPR

EOS
24

This hybridization scheme is useful in describing

triple covalent bonds
The geometric distribution of the two sp hybrid
orbitals is on a line, directed at 180o angles
This
distribution
gives a
linear
molecular
geometry
EOS
25

This hybridization allows for expanded valence shell

compounds typical for group 5A elements, e.g., P
A 3s electron can
be promoted to a
3d subshell, which
gives rise to a set
of five sp3d hybrid
orbitals

EOS
26

This hybridization allows for expanded valence shell

compounds typically group 6A elements, e.g., S
A 3s and a 3p
electron can be
promoted to the 3d
subshell, which
gives rise to a set
of six sp3d2
hybrid orbitals

EOS
27

In hybridization schemes, one hybrid orbital is

produced for every simple atomic orbital involved
Write a plausible Lewis structure for the molecule
or ion
Use the VSEPR method to predict the electrongroup geometry of the central atom
Select the hybridization scheme that corresponds to
the VSEPR prediction
Describe the orbital overlap and molecular
geometry

EOS
28

EOS
29

Covalent bonds formed by the end-to-end overlap

of orbitals, regardless of orbital type, are called
sigma () bonds. All single bonds are sigma bonds
A bond formed by parallel, or side-by-side,
orbital overlap is called a pi () bond
A double bond is made
up of one sigma bond
and one pi bond

A triple bond is made up

of one sigma bond and
two pi bonds
EOS
30

A double bond is
made up of one
sigma bond and one
pi bond

EOS
31

EOS
32

Geometric isomers are isomers that differ only in

the geometric arrangement of certain substituent
groups

Each compound is distinctly different in

both physical and chemical properties
EOS
33

Molecular orbitals (MOs) are mathematical

equations that describe the regions in a molecule
where there is a high probability of finding
electrons
Molecular orbitals (MOs) are essentially
combinations of atomic orbitals two types
exist, bonding and antibonding orbitals
Molecular orbitals (MOs) are built up (Aufbau
principle) in the same way as atomic orbitals
EOS
34

The hydrogen molecule

Antibonding MO = region
of diminished electron
density
Bonding MO =
enhanced region of
electron density

EOS
35

EOS
36

Antibonding MOs
= higher energy
and MOs

Bonding MOs
s AOs = MOs
p AOs = MOs
EOS
37

38

EOS
39

Those diatomic molecules containing atoms of

different elements. Examples are HCl, CO, CN- and
NO.
To draw the molecular orbital diagrams for
heteronuclear diatomic molecules, we face a new
problem: where do we place the atomic orbitals on an
atom relative to atomic orbitals on other atoms? For
example, how can we predict whether a carbon 2s or
an oxygen 2s orbital is lower in energy?
The answer comes from our understanding of
electronegativity. Oxygen is more electronegative
than carbon. The more electronegative element's
orbitals are placed lower on the molecular orbital
diagram than those of the more electropositive
element.
40

*2p

2p

Energy

2p

2p
2p
p

*2s

2s

2s

s
C

CO molecule

CN- molecule

N
41

*2p

2p

Energy

2p

p
2p
2p
2s

*2s
2s

s
N

NO molecule

O
42

*sp
x
y 3p
z

Energy

nonbonding
py

pz

1s
sp
3s

nonbonding
s
H

HCl molecule

Cl
43

Consider the HCl molecule. Combination between the

hydrogen 1s AO and the chlorine 1s, 2s, 2p and 3s orbitals
can be ruled out because their energies are too low.
If overlap occurred between the chlorine 3py and 3pz
orbitals it would be non-bonding because the positive lobe
of hydrogen will overlap equally with the positive and
negative lobes of the chlorine orbitals.
The combination of H, 1s1, and Cl, 3px1, gives both bonding
and antibonding orbitals, and the two electrons occupy the
bonding MO, leaving the antibonding MO empty.
It is assumed that all the chlorine AOs except 3px are
localized on the chlorine atom and retain their original AO
status, and the 3s, 3py and 3pz orbitals are regarded as
non-bonding lone pairs.

44

The VSEPR method is used to predict the

shapes of molecules and polyatomic ions
If all electron groups are bonding groups, the
molecular geometry is the same as the
electron-group geometry
A polar covalent bond has separate centers
of positive and negative charge, creating a
bond dipole

EOS
45

In the valence bond theory, a covalent bond

is formed by the overlap of atomic orbitals of
the bonded atoms in a region between the
atomic nuclei
Hybridized orbitals include sp, sp2, sp3, sp3d,
and sp3d2

Unhybridized p orbitals overlap in a side-byside fashion to form bonds

EOS
46

Single bonds are all hybridized bonds,

double bonds have one bond and one
bond, and triple bonds have one bond and
two bonds
In molecular orbital theory, atomic orbitals of
separated atoms are combined into
molecular orbitals
The benzene molecule is usually represented
by its resonance hybrid
Benzene-like compounds are called aromatic
compounds

EOS
47