ORBITALS

and
MOLECULAR
REPRESENTATION

by
DR. STEPHEN THOMPSON
MR. JOE STALEY

The contents of this module were developed under grant award # P116B-001338 from the Fund for the Improve-
ment of Postsecondary Education (FIPSE), United States Department of Education.
However, those contents do not necessarily represent the policy of FIPSE and the Department of Education, and
you should not assume endorsement by the Federal government.
ORBITALS AND MOLECULAR REPRESENTATION
CONTENTS

2 Atomic Orbitals (n = 1)
3 Atomic Orbitals (n = 2)
4 Atomic orbitals (n = 3)
5 Hybrid Atomic Orbitals (sp)
6 Hybrid Atomic orbitals (sp2)
7 Hybrid Atomic Orbitals (sp2)
8 Hybrid Atomic Orbitals (sp3)
9 Overlapping Orbitals (Bonding And Antibonding)
10 Orbital Pictures For H And H2
11 Difluorine
12 Carbon Orbitals (Methane And Ethane)
13 Carbon Orbitals (Ethene)
14 Carbon Orbitals (Ethene)
15 Carbon Orbitals (Ethyne)
16 Carbon Orbitals (Ethyne)
17 Carbon Orbitals (Benzene)
18 Carbon Orbitals (Benzene)
19 Several Representations Of Molecules
20 Several Representations Of Benzene
21 Representations Of Molecules
22 Representations Of Molecules
23 Representations Of Molecules
ORBITALS AND MOLECULAR REPRESENTATION
ATOMIC ORBITALS

While Lewis diagrams and energy level structures can

show connectivity and energy relationships of mol-
ecules, they do not show the shape of the molecules.
For this we need to picture atomic and molecular orbitals.

n=1
l=0
1s
The picture above shows the spherically symmetric 1s
orbital in the ‘green’ phase. Sometimes it is more con-
venient not to show the phase, in which case we can
use a greyed representation, as shown below..
We denote the phase of the wave function by color,
using light red for one phase and green for the opposite
phase. Many books assign these phases plus or minus
signs but the only real meaning is that they are oppo-
site. Neither phase is plus or minus anything on its own
but they are only opposite to each other. Sometimes
when we are not concerned with phase we will draw
the orbitals as a slightly reddish gray.

1s

It is also possible to show the orbital as a simple loop.

Here are some boxes for you to practice drawing
s orbitals in, although you do not really need boxes.
1s

And if you are drawing his by hand, the loop does not
have to be an exact circle.

1s

As we proceed developing atomic and molecular orbit-

als we will show various forms of representation.

n=2

You can draw the two loops

for 2s in the box below.

l=0
2s

2
ORBITALS AND MOLECULAR REPRESENTATION
ATOMIC ORBITALS

n=2
l=1
2px

This is an accurate This is a common This simplified px orbital A hand drawn version does
representation of a picture of a px orbital is often useful. not have to be exact.
2px orbital.

2py

Use this box

2pz to draw a pz
orbital.

We can combine all three p orbitals in a three

dimensional display.

y
y
y

x x x

z z
z

Use these axes to draw all

three p orbitals.
3
ORBITALS AND MOLECULAR REPRESENTATION
ATOMIC ORBITALS
n=3

3s Draw the
3s orbital
l=0 in the box
at left.

Phase Picture Grayscale Loop Diagram

3px

l=1

3py

3pz

l=2

3dxy 3dxz 3dyz 3dx2--y2 3dz2

3dxy 3dxz 3dyz 3dx2--y2 3dz2

4
ORBITALS AND MOLECULAR REPRESENTATION
HYBRID ATOMIC ORBITALS
sp
sp orbitals are a combination, or hybrid, of an s and a p You will recall that our color convention is to show the
orbital. In addition there will be two remaining unhy- phases of the atomic orbitals with red and green. We
bridized p orbitals orthogonal to each other and to the shall show the phases of hybrid orbitals in blue and
line joining the two hybrid sp orbitals. yellow.

+ +

2s 2p sp sp 2 x sp
You will also see these orbitals in greyscale, without phases.
We use reddish grey for unhybridized orbitals and plain gray
for for hybridized orbitals.

2p sp sp 2 x sp
2s It is common to show hybrid orbitals
We can also draw these orbitals as simplified loops. without the small lobes.

+ +

2s 2p sp sp 2 x sp

It is useful to draw the sp hybrid orbitals yourself.

An sp hybridized atom uses one s and one p orbital to
make two sp hybrid orbitals; there are two remaining p
orbitals.
Next we show the phase pictures of combining the
sp hybrid orbitals with first one and then both of the Axes for you
remaining p orbitals. to draw the
loop diagram.
Phase pictures. loop Diagram

2 x sp + 2p 2 x sp + 2 x 2p 2 x sp + 2 x 2p
NOTE: When we write 2 x sp we mean two instances
of sp and when we write 2p we mean one instance of a
2p orbital.
5
ORBITALS AND MOLECULAR REPRESENTATION
HYBRID ATOMIC ORBITALS

sp2
The pictures below
sp2 hybrid orbitals are formed when are trigonal views of
one 2s orbital combines or hybridizes sp2 sp2. Trigonal means
with two 2p orbitals in the shapes and arranged in triangular
arrangement shown. form in a plane.

+ +

2s 2p 2p
sp2

trigonal view of sp2

120º
sp2
In greyscale:
120º

120º

+ +

2s 2p 2p

You will often see a simple presentation of the sp2 orbitals. You can also draw the sp2 hy-
Thr important points to know about are that the three brid orbital as simple loops.
bonds are in a plane and that they are 120˚ apart.

Draw the loop version of

the trigonal set of sp2 orbit-
als in the box at right.

6
ORBITALS AND MOLECULAR REPRESENTATION
HYBRID ATOMIC ORBITALS

sp2
In addition to the trigonal set of hybridized orbitals there
is a remaining 2p orbital that will point above and below
the trigonal plane.

First we show the phase orbitals.

planar view of sp2 2p sp2 + 2p

Here we show the grayscale.

120°
120°
x

120°
y

7
ORBITALS AND MOLECULAR REPRESENTATION
HYBRID ATOMIC ORBITALS

sp3

sp3 orbitals are formed by the hybridization of a 2s

orbital and three 2p orbitals.

2s
sp3

2p

2p

+ sp3
sp3

sp3
2p

sp3 orbitals have a tetrahedral structure.

8
ORBITALS AND MOLECULAR REPRESENTATION
OVERLAPPING ORBITALS

BONDING ORBITALS ANTIBONDING ORBITALS

Chemical bonds are formed from the overlapping of Overlapping orbitals of opposite phase form antibond-
atomic orbitals having the same phase. ing orbitals.

s+sσ s - s σ*

s+pσ s - p σ*

p+pσ p - p σ*

p+pπ p - p π*

9
ORBITALS AND MOLECULAR REPRESENTATION
ORBITAL PICTURES FOR H AND H2

We can also make orbital energy levels for molecules.

HYDROGEN ORBITAL

or

1s 1s

ANTIBONDING ORBITAL

ENERGY
1sA - 1sB

1sA - 1sB 1sA - 1sB

1sA 1sB

BONDING ORBITAL

1sA + 1sB

HA H2 HB

1sA + 1sB 1sA + 1sB

10
ORBITALS AND MOLECULAR REPRESENTATION
DIFLUORINE

2pA - 2pB
σ*
ENERGY

z y x x y z
2pA5 2pB5
σ
2sA2 2sB2
2pA + 2pB

1sA2 1sB2
1
FA FB

In picture 1 we show the molecular orbital structure of F2.

In picture 2 we show the overlapping p orbitals, which
form the bond between the two fluorine atoms, in red and
green gradients.

The dashed lines show the remaining p orbitals which do

not take part in the bonding. 2

z z

Construct the molecular orbital diagram for dichlorine.

x

y y
3
Showing the p orbitals.

z z

y y
4
Showing the s and p orbitals.

11
ORBITALS AND MOLECULAR REPRESENTATION
CARBON ORBITALS

METHANE AND ETHANE

C
H H
H

1
Methane CH4
In methane and ethane, all of the
bonds are σ−bonds, which means that
they are formed by orbitals overlapping
along a direct line between the nuclei
of the two bonding atoms.

H H

H C C H C 2H 6

H H

2
Ethane CH6

Color conventions:
Hydrogen atoms are shown in gray.
Hybrid atomic orbitals are shown in blue and yellow.
Atomic p orbitals are shown in red and green.
Greyscale Conventions:
Hybrid orbitals are shown in grey.
Unhybridized atomic orbitals are shown in reddish-grey.

12
ORBITALS AND MOLECULAR REPRESENTATION
CARBON ORBITALS
ETHENE C 2H 4

� ����

� �

3
Picture 3 shows the sigma bond formed by overlaping
sp2 orbitals between the two carbon atoms of ethene.
The other sp2 orbitals are shown in dashed outline.

� ����

� �

4
Picture 4 shows the π bond between the p orbitals of
the carbon atoms. The pi bond is the overlap of the
two red spheres and is actually coming out of the plane
of the paper.

900 rotation

5
Picture 5 is similar to picture 4 but rotated 900 around
the σ bond, so that the overlapping p orbitals which
form the π bond are shown with the red phase above
the σ bond and with the green phase below.

13
ORBITALS AND MOLECULAR REPRESENTATION
CARBON ORBITALS

ETHENE C 2H 4

Ethene from above the trigonal plane. The carbon

atoms and orbitals are shown.

H H
C 2H 4
C C

H H

Ethene from above the trigonal plane with the hydrogen 900 rotation
atoms shown. The bond angles and relative bond
lengths are correct.

H H
C C
H H

Ethene in the trigonal plane.

14
ORBITALS AND MOLECULAR REPRESENTATION
CARBON ORBITALS

ETHYNE C 2H 2

� ����

� �

9
This drawing shows the sigma bond between two
carbon atoms.

� ����

� �

10
In this drawing we have added a pi bond to the ethyne.

� ����

� �

11
We have added the other π bond which, as it needs
to be orthogonal to both the first π bond and to the σ
bond, must be imagined as coming out of the paper.

15
ORBITALS AND MOLECULAR REPRESENTATION
CARBON ORBITALS

ETHYNE C 2H 2

12

Ethyne in the trigonal plane, but with the hydrogen

atoms added.

H C C H

13
Unlike ethene, ethyne has the same form and ap-
pearance when rotated 900 around the C-C axis.

16
ORBITALS AND MOLECULAR REPRESENTATION
CARBON ORBITALS

BENZENE C 6H 6

C C

C C

14 15
The sigma bond ring of benzene. The sigma bond ring of benzene
with the additional sp2 orbitals.
C C
This is the ring of σ bonds
whose orbitals are shown in
picture 15

C C C C

C C ↔C C

C C C C
This is a former represen-
tation of the resonance
structure of benzene.

This is a contemporary
representation of the
resonance structure of
benzene.

17
ORBITALS AND MOLECULAR REPRESENTATION
CARBON ORBITALS
BENZENE C 6H 6

16
To which we have now added
the pi orbitals above the ring.

900 rotation

17
Benzene carbon orbitals viewed from the side.
This picture illustrates the delocalization of
the six 2p electrons in the benzene molecule.
These six electons are shared collectively
among all six of the carbon atoms.

900 rotation

19
18
Benzene from the side, complete with hydrogen atoms.
Adding the hydrogen atoms to picture 16 we
view benzene from above, complete.
18
ORBITALS AND MOLECULAR REPRESENTATION
SEVERAL REPRESENTATIONS OF MOLECULES
METHANE CH4
H
95nm 109.5º
C
H H
H

All orbitals Textbook Structural Space Ball and

tetrahedron filling stick
ETHANE C 2H 6
109 nm 154 nm
H H
H C C H

H 111º H
All orbitals Textbook orbitals Structural Space Ball and
filling stick
ETHENE C 2H 4

134 nm
All orbitals Textbook orbitals H H
looking down on the trigonal plane
C C 120°

H 120° H
Space Ball and
Structural filling stick

All orbitals but no Textbook orbitals

hydrogen (for clarity)
Looking along the trigonal plane

ETHYNE C 2H 2

Textbook orbitals
All orbitals Space Ball and
106 nm 120 nm filling stick

H C C H
Structural

19
ORBITALS AND MOLECULAR REPRESENTATION
SEVERAL REPRESENTATIONS OF BENZENE
BENZENE C 6H 6

Benzene showing all orbitals Benzene textbook Benzene textbook

σ bonds σ and π bonds
from the side

Benzene space filling Benzene ball and stick

H H 140 nm
110 nm
C C C C

C 120º C H C C H

C C C C

H H

Benzene structural Benzene structural carbon ring

carbon ring and hydrogens

20
ORBITALS AND MOLECULAR REPRESENTATION
REPRESENTATIONS OF MOLECULES
You can easily draw orbitals, bonds and molecules.

Start by drawing a circle, like this: You draw a circle (an s orbital) in
the box.

This is an s orbital.

Now draw one circle above You draw a p orbital.

another one, like this: (two circles tangent)

This is a p orbital.

When two s orbitals from different atoms overlap, this is You draw two overlapping circles in the box below.
called a σ (sigma) bond. This is a σ bond.

When an s and a p orbital overlap, this is a σ bond. You can draw the s and p overlap.

21
ORBITALS AND MOLECULAR REPRESENTATION
REPRESENTATIONS OF MOLECULES

DINITROGEN N2
110 nm

N N
Textbook orbitals Structural
Ball and stick
Space filling
All bonding orbitals

DIOXYGEN O2
π bond

Space filling
π bond
For clarity, only the orbitals which 121 nm
form the π bonds are shown.
O O
Ball and stick
Structural

SIMPLIFIED ORBITALS

We have shown molecular pictures which

are as accurate as possible, however such
orbitals are difficult to draw by hand. But a
simplified version of them is easy to draw an s orbital
and shows much about mjolecular structure a px orbital
and bonding.

+z

-y a pz orbital a py orbital

Draw the bonding orbitals for:

-x +x
H 2O

NH3
+y
-z
CO
All three p orbitals
CO2

22
ORBITALS AND MOLECULAR REPRESENTATION
REPRESENTATIONS OF MOLECULES

There are three orthogonal p orbitals. They can be

drawn like this. Draw your own set of p orbitals on the axes pro-
vided.

Two p orbitals (on different atoms) in the same direction You draw two p orbitals side by side and overlapping,
can overlap forming a π (pi) bond. forming a π bond.

You can draw hybrid orbitals like this:

You draw an sp hybridized atom in the box below.

You draw an sp2 hybridized atom.

23