GROUP THEORY

CHAPTER OVERVIEW

Group Theory
Symmetry is very important in chemistry researches and group theory is the tool that is used to determine symmetry. Usually, it is
not only the symmetry of molecule but also the symmetries of some local atoms, molecular orbitals, rotations and vibrations of
bonds, etc. that are important.
Group Theory: Theory
Group Theory and its Application to Chemistry
Understanding Character Tables of Symmetry Groups
Woodward-Hoffmann rules

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Group Theory: Theory
Symmetry can help resolve many chemistry problems and usually the first step is to determine the symmetry. If we know how to
determine the symmetry of small molecules, we can determine symmetry of other targets which we are interested in. Therefore, this
module will introduce basic concepts of group theory and after reading this module, you will know how to determine the
symmetries of small molecules.

Introduction
Symmetry is very important in chemistry researches and group theory is the tool that is used to determine symmetry. Usually, it is
not only the symmetry of molecule but also the symmetries of some local atoms, molecular orbitals, rotations and vibrations of
bonds, etc. that are important. For example, if the symmetries of molecular orbital wave functions are known, we can find out
information about the binding. Also, by the selection rules that are associated with symmetries, we can explain whether the
transition is forbidden or not and also we can predict and interpret the bands we can observe in Infrared or Raman spectrum.
Symmetry operations and symmetry elements are two basic and important concepts in group theory. When we perform an
operation to a molecule, if we cannot tell any difference before and after we do the operation, we call this operation a symmetry
operation. This means that the molecule seems unchanged before and after a symmetry operation. As Cotton defines it in his book,
when we do a symmetry operation to a molecule, every points of the molecule will be in an equivalent position.

Symmetry Elements
For different molecules, there are different kinds of symmetry operations we can perform. To finish a symmetry operation, we may
rotate a molecule on a line as an axis, reflect it on a mirror plane, or invert it through a point located in the center. These lines,
planes, or points are called symmetry elements. There may be more then one symmetry operations associated with a particular
symmetry
Identity E
The molecule does not move and all atoms of the molecule stay at the same place when we apply an identity operation, E, on it. All
molecules have the identity operation. Identity operation can also be a combination of different operations when the molecule
returns to its original position after these operations are performed.1 This will be demonstrated later.
Proper Rotations and Cn axis

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Group Theory and its Application to Chemistry
Group Theory is the mathematical application of symmetry to an object to obtain knowledge of its physical properties. What group
theory brings to the table, is how the symmetry of a molecule is related to its physical properties and provides a quick simple
method to determine the relevant physical information of the molecule. The symmetry of a molecule provides you with the
information of what energy levels the orbitals will be, what the orbitals symmetries are, what transitions can occur between energy
levels, even bond order to name a few can be found, all without rigorous calculations. The fact that so many important physical
aspects can be derived from symmetry is a very profound statement and this is what makes group theory so powerful.

Introduction
To a fully understand the math behind group theory one needs to take a look at the theory portion of the Group Theory topic or
refer to one of the reference text listed at the bottom of the page. Never the less as Chemist the object in question we are examining
is usually a molecule. Though we live in the 21st century and much is known about the physical aspects that give rise to molecular
and atomic properties. The number of high level calculations that need to be performed can be both time consuming and tedious.
To most experimentalist this task is takes away time and is usually not the integral part of their work. When one thinks of group
theory applications one doesn't necessarily associated it with everyday life or a simple toy like a Rubik's cube. A Rubik's cube is an
a cube that has a 3 × 3 array of different colored tiles on each of its six surfaces, for a total of 54 tiles. Since the cube exist in 3D
space, the three axis are x, y , z . Since the rubik's cube only allows rotation which are called operations, there are three such
operations around each of the x, y , z axis.

Figure: Reubik's cube. Use with permission from Wikipedia

Of course the ultimate challenge of a Rubik's cube is to place all six colors on each of the six faces. By performing a series of such
operations on the Rubik's cube one can arrive at a solution (A link of a person solving a Rubik's cube1 in 10.4s with operations
performed noted, the operations performed will not translate to chemistry applications but it is a good example of how symmetry
operations arrive at a solution). The operations shown in the Rubik's cube case are inherent to the make up of the cube, i.e., the only
operations allowed are the rotations along the x, y, z axis. Therefore the Rubik's cube only has x,y,z rotation operations. Similarly
the operations that are specific to a molecule are dependent on its symmetry. These operations are given in the top row of the
character table.

rotation and quadratic

C3v E 2C3 3σv
translation functions

A1 +1 +1 +1 z
2
x +y
2
,z 2

A2 +1 +1 -1 Rz -

(x2
−y
2
, xy) (xz,
E +2 -1 0 (x , y ) (R , R )
x y
yz )

The character table contains a wealth of information, for a more detailed discussion of the character table can be found in Group
Theory Theoretical portion of the chemWiki. All operations in the character table are contained in the first row of the character
table, in this case E , C , & σ , these are all of the operations that can be preformed on the molecule that return the original
3 v

structure. The first column contains the three irreducible representations from now on denoted as Γ , here they are A , A & E .
ir 1 2

The value of the Γ denotes what the operation does. A value of 1 represents no change, -1 opposite change and 0 is a combination
ir

of 1 & -1 (0’s are found in degenerate molecules. The final two columns Rotation and Translation represented by R ,R , R & x, x y z

y , z respectively. Where R's refer to rotation about an axis and the x, y , z refers to a translation about an axis, the Γ the each R ,
ir x

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Ry, R & x, y , z term is the irreducible symmetry of a rotation or translation operation. Like wise the final column the orbital
z

symmetries relates the orbital wavefunction to a irreducible representation.

Direct Products
This is a quick rule to follow for calculating Direct Products of irreproducible representations, such a calculation will be necessary
for working through transition moment integrals. Following the basic rules given by the table given below. One can easily work
through symmetry calculations very quickly.

"Symmetric" × "Symmetric" is "Symmetric" × "AntiSymmetric" "AntiSymmetric" × "Symmetric" "AntiSymmetric" ×

"Symmetric" is "AntiSymmetric" is "AntiSymmetric" "AntiSymmetric" is "Symmetric"

g× g = g g× u = u u ×g = u u ×u = g

′ ′ ′ ′ ′′ ′′ ′′ ′ ′′ ′′ ′′ ′
× = × = × = × =

A ×A = A A ×B = B B ×A = B B ×B = A

Vibrations
All molecules vibrate. While these vibrations can originate from several events, which will be covered later, the most basic of these
occurs when an electron is excited within the electronic state from one eigenstate to another. The Morse potential (electronic state)
describes the energy of the eigenstate as a function of the interatomic distance. When an electron is excited form one eigenstate to
another within the electronic state there is a change in interatomic distance, this result in a vibration occurring.

Vibrational energies arise from the absorption of polarizing radiation. Each vibrational state is assigned a Γ . A vibration occurs
ir

when an electron remains within the electronic state but changes from one eigenstate to another (The vibrations for the moment are
only IR active vibrations, there are also Raman vibrations which will be discussed later in electronic spectroscopy), in the case of
the Morse diagram above the eigenstates are denoted as ν . As you can see from the diagram the eigenstate is a function of energy
versus interatomic distance.
To predicting whether or not a vibrational transition, or for that matter a transition of any kind, will occur we use the transition
moment integral.

∫ Ψi ∗ μΨf dτ = ⟨Ψi |μ| Ψf ⟩ (1)

The transition moment integral is written here in standard integral format, but this is equivalent to Bra & Ket format which is
standard in most chemistry quantum mechanical text (The ⟨Ψ | is the Bra portion, |Ψ ⟩ is the Ket portion). The transition moment
i f

operator μ is the operator the couples the initial state Ψ to the final state Ψ , which is derived from the time independent
i f

Schrödinger equation. However using group theory we can ignore the detailed mathematical methods. We can use the Γ of the ir

vibrational energy levels and the symmetry of the transition moment operator to find out if the transition is allowed by selection
rules. The selection rules for vibrations or any transition is that is allowed, for it to by allowed by group theory the answer must
contain the totally symmetric Γ , which is always the first Γ in the character table for the molecule in question.
ir ir

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Symmetry
Let’s work through an example: Ammonia (N H ) with a C
3 3v symmetry. Consequently, all of the properties contained in the C3v

character table above are pertinent to the ammonia molecule.

The principle axis is the axis that the highest order rotation can be preformed. In this case the z-axis pass through the lone pairs
(pink sphere), which contains a C axis. The ?’s or mirror planes (σ parallel to z-axis & σ perpendicular to the z-axis). In
3 v h

ammonia there is no σ only three σ ’s. The combination of C & σ leads to C point group, which leads to the C3v character
h v 3 v 3v

table.
The number of transitions is dictated by 3N-6 for non-linear molecules and 3N-5 for linear molecules, where N is the number of
atoms. The 6 & the 5 derive from three translations in the x,y,z plan and three rotations also in the x,y,z plan. Where a linear
molecule only has two rotations in the x & y plans since the z axis has infinite rotation. This leads to only 5 degrees of freedom in
the rotation and translation operations. In the case of Ammonia there will be 3(4)-6=6 vibrational transitions. This can be
confirmed by working through the vibrations of the molecule. This work is shown in the table below.

The vibrations that are yielded 2A1 & 2E (where E is doubly degenerate, meaing two vibration modes each) which total 6
vibrations. This calculation was done by using the character table to find out the rotation and translation values and what atoms
move during each operation. Using the character table we can characterize the A1 vibration as IR active along the z-axis and raman
active as well. The E vibration is IR active along both the x & y axis and is Raman active as well. From the character table the IR
symmetries correspond to the x, y & z translations. Where the Raman active vibrations correspond to the symmetries of the d-
orbitals.

Vibrational Spectroscopy
Infrared Spectroscopy
Infrared Spectroscopy (IR) measures the vibrations that occur within a single electronic state, such as the one shown above.
Because the transition occurs within a single electronic state there is a variation in interatomic distance. The dipole moment is
dictate by the equation.
⃗ 
μ⃗ = α E (2)

Where μ⃗  is the magnitude of dipole moment; α is the polarizability constant (actually a tensor) & E is the magnitude of the
electric field which can be described as the electronegitivity.3 Therefore when a vibration occurs within a single electronic state
there is a change in the dipole moment, which is the definition of an active IR transition.
dμ
( ) ≠0 (3)
dq
eq

In terms of group theory a change in the dipole is a change from one vibrational state to another, as shwon by the equation above. A
picture of the vibrational states with respect ot the rotational states and electronic states is given below. In IR spectroscopy the
transition occurs only from on vibrational state to another all within the same electronic state, shown below as B.

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Electronic Transitions
When an electron is excited from one electronic state to another, this is what is called an electronic transition. A clear example of
this is part C in the energy level diagram shown above. Just as in a vibrational transition the selection rules for electronic transitions
are dictated by the transition moment integral. However we now must consider both the electronic state symmetries and the
vibration state symmetries since the electron will still be coupled between two vibrational states that are between two electronic
states. This gives us this modified transition moment integral:

Where you can see that the symmetry of the initial electronic state & vibrational state are in the Bra and the final electronic and
vibrational states are in the Ket. Though this appears to be a modified version of the transition moment integral, the same equation
holds true for a vibrational transition. The only difference would be the electronic state would be the same in both the initial and
final states. Which the dot product of yields the totally symmetric representation, making the electronic state irrelevant for purely
vibrational spectroscopy.

Raman
In Resonance Raman spectroscopy transition that occurs is the excitation from one electronic state to another and the selection
rules are dictated by the transition moment integral discussed in the electronic spectroscopy segment. However mechanically
Raman does produce a vibration like IR, but the selection rules for Raman state there must be a change in the polarization, that is
the volume occupied by the molecule must change. But as far as group theory to determine whether or not a transition is allowed
one can use the transition moment integral presented in the electronic transition portion. Where one enters the starting electronic
state symmetry and vibrational symmetry and final electronic state symmetry and vibrational state, perform the direct product with
the different M's or polarizing operators For more information about this topic please explore the Raman spectroscopy portion of
the Chemwiki

Fluorescence
For the purposes of Group Theory Raman and Fluorescence are indistinguishable. They can be treated as the same process and in
reality they are quantum mechanically but differ only in how Raman photons scatter versus those of fluorescence.

Phosphorescence
Phosphorescence is the same as fluorescence except upon excitation to a singlet state there is an interconversion step that converts
the initial singlet state to a triplet state upon relaxation. This process is longer than fluorescence and can last microseconds to
several minutes. However despite the singlet to triplet conversion the transition moment integral still holds true and the symmetry
of ground state and final state still need to contain the totally symmetric representation.

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Molecular Orbital Theory and Symmetry
Molecular Orbitals also follow the symmetry rules and indeed have their own ?ir. Below are the pi molecular orbitals for trans-2-
butene and the corresponding symmetry of each molecular orbital.

The ?ir of the molecular orbitals are created by simply preforming the operations of that molecule's character table on that orbital.
In the case of trans-2-butene the point group is C2h, the operations are: E, C2, i & ?h. Each operation will result in a change in
phase (since were dealing with p-orbitals) or it will result in no change. The first molecular orbital results in the totally symmetric
representation, working through all four operations E, C2, i, ?h will only result in 1's meaning there is no change, giving the Ag
symmetry state. These molecular orbitals also represent different electronic states and can be arranged energetically. Putting the
orbital that has the lowest energy, the orbital with the fewest nodes at the bottom of the energy diagram and like wise working up
form lowest energy to highest energy. The highest energy orbital will have the most nodes. Once you've set up your MO diagram
and place the four pi electrons in the orbitals you see that the first two orbitals listed (lowest energy) are HOMO orbitals and the
bottom two (highest energy) and LUMO orbitals. With this information if you have a transition from the totally symmetric HOMO
orbital to the totally symmetric LUMO orbital the transition moment operator would need to have Ag symmetry (using the C2h) to
give a result containing the totally symmetric representation.
These four molecular orbitals represent four different electronic states. So transitions from one MO into another would be
something that is measured typically with UV-Vis spectrometer.

References and Further Reading

1. Daniel Harris & Michael Bertolucci Symmetry and Spectroscopy New York, Dover Publications 1989 ($19.95), [Highly
recommended, great text for explaining Group Theory for molecules and Application of Group Theory in various
spectroscopy's]
2. Albert Cotton Chemical Applications of Group Theory 3rd New York, Wiley Inter-science Publication 1990 ($148.50),
[Mathematical approach to group theory in chemistry]
3. Donald A. McQuarrie Quantum Chemistry Sausalito, University Science Books 1983 ($88.00) [Classic Quantum chemistry text
very clear and thorough]
4. Douglas Skoog, James Holler & Stanley Crouch Principles of Instrumental Analysis (6th ed) Thomson Brooks Cole 2007
($170.04), [Covers basics of all types of analytical chemistry methods and theory]

Problems
1. Follow the links above to Water, Ammonia and Benzene and work out the ?ir of the vibrations. Using the method laid out by the
character table. (Follow the example of ammonia for help)
2. From problem 1. work out what possible are the possible transition moment operators for each vibration.

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 3. Work through the P-orbital molecular orbitals for cis-butadiene. (Note the conservation of "stuff", start by combining four p-
orbitals and finish with four molecular orbitals) What is the point group? what are the ?ir of each MO? Finally how many
vibrations are there for cis-butadiene and what are their ?ir.

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Understanding Character Tables of Symmetry Groups
Every molecule has a point group associated with it, which are assigned by a set for rules (explained by Group theory). The
character tables takes the point group and represents all of the symmetry that the molecule has.
Symbols under the first column of the character tables

(singly degenerate or one dimensional) symmetric with respect to

A (Mulliken Symbol)
rotation of the principle axis
(singly degenerate or one dimensional) anti-symmetric with respect to
B (Mulliken Symbol)
rotation of the principle axis

E (Mulliken Symbol) (doubly degenerate or two dimensional)

T (Mulliken Symbol) (thirdly degenerate or three dimensional )

symmetric with respect to the Cnprinciple axis, if no perpendicular axis,

Subscript 1
then it is with respect to σv
anti-symmetric with respect to the Cnprinciple axis, if no perpendicular
Subscript 2
axis, then it is with respect to σv

Subscript g symmetric with respect to the inverse

subscript u anti-symmetric with respect to the inverse

prime symmetric with respect to σ (reflection in horizontal plane)

h

anti-symmetric with respect to σ ( opposite reflection in horizontal

double prime h

plane)

Symbols in the first row of the character tables

E describes the degeneracy of the row (A and B= 1) (E=2) (T=3)

2pi/n= number of turns in one circle on the main axis without changing
Cn
the look of a molecule (rotation of the molecule)
2π/n= number of turns in one circle perpendicular to the main axis,
Cn'
without changing the structure of the molecule
2π/n= number of turns in one circle perpendicular to the Cn' and the
Cn"
main axis, without changing the structure

σ' reflection of the molecule perpendicular to the other sigma

reflection of the molecule vertically compared to the horizontal highest

σv (vertical)
fold axis.
reflection of the molecule horizontally compared to the horizontal
σh or d (horizontal)
highest fold axis.

i Inversion of the molecule from the center

rotation of 2π/n and then reflected in a plane perpendicular to rotation

Sn
axis.

#Cn the # stands for the number of irreducible representation for the Cn

#σ the # stands for the number irreducible representations for the sigmas.

in the same rotation there is another rotation, for instance Oh has

the number in superscript
3C2=C42

other useful definitions

(Rx,Ry) the ( , ) means they are the same and can be counted once.

x2+y2, z2 without ( , ) means they are different and can be counted twice.

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Looking at a Character Table
D3h E 2C3 3C2 σh 2S3 3σv IR Raman

A1' 1 1 1 1 1 1 x2+y2, z2

A2' 1 1 -1 1 1 -1 Rz

E' 2 -1 0 2 -1 0 (x,y) (x2-y2, xy)

A1" 1 1 1 -1 -1 -1

A2" 1 1 -1 -1 -1 1 z

E" 2 -1 0 -2 1 0 (Rx, Ry) (xy, yz)

The order is the number in front of the the classes. If there is not number then it is considered to be one. The number of classes is
the representation of symmetries.The D3h has six classes and an order of twelve.

Understanding using matrix

The identity does nothing to the matrix.
[1 0 0] [X] [X]
[0 1 0] [Y] = [Y]
[0 0 1] [Z] [Z]
σ(xy) the x and y stay positive, while z turns into a negative.
[1 0 0] [X] [X]
[0 1 0] [Y] = [Y]
[0 0 -1] [Z] [-Z]
Inversion (I) is when all of the matrix turns into a negative.
[-1 0 0] [X] [-X]
[0 -1 0] [Y] = [-Y]
[0 0 -1] [Z] [-Z]
Cnis when one would use cos and sin. for an example C4
[cos (2π/4 -sin (2π/4 0] [X] []
[sin (2π/4) cos (2π/4) 0] [Y] = []
[0 0 1] [Z] []

References
1. R. S. Mulliken, J. Chem. Phys., 1955, 23, 1997; 1956, 24, 1118

Practice
There are two columns on the far right. One is ir and the other is Raman. Try moving the molecule around using reflections and
rotations. Remember when the positive side of the orbitals goes into the negative side, the number is negative (in the character
tables). Also, remember if it is moved or reflected and there is no change then the number is positive (in the character tables). also,
molecules are placed on a x, y, and z (three dimensional) graph. The highest C fold rotation is always on the z axis.

IR

Px

Py

Pz

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 Rx

Ry

Rz

Raman

dxy

dyz

dxz

dz 2

dx2 −y 2

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Woodward-Hoffmann rules
The Woodward-Hoffman rules (R. B. Woodward was one of the U.S.'s most successful and renowned organic chemists; Roald
Hoffmann is a theoretical chemist. Hoffmann shared the 1981 Nobel Prize with Kenichi Fukui) allow us to follow the symmetry of
the occupied molecular orbitals along a suggested reaction path connecting reactants to products and to then suggest whether a
symmetry-imposed additional energy barrier (i.e., above any thermodynamic energy requirement) would be expected. For example,
let us consider the disrotatory closing of 1,3-butadiene to produce cyclobutene. The four p orbitals of butadiene, denoted π 1

through π in the figure shown below, evolve into the σ and σ and π and π orbitals of cyclobutene as the closure reaction
4
∗ ∗

proceeds. Along the disrotatory reaction path, a plane of symmetry is preserved (i.e., remains a valid symmetry operation) so it can
be used to label the symmetries of the four reactant and four product orbitals. Labeling them as odd (o) or even (e) under this plane
and then connecting the reactant orbitals to the product orbitals according to their symmetries, produces the orbital correlation
diagram shown below.

Figure: Professor Roald Hoffmann (right)

The four π electrons of 1,3-butadiene occupy the π and π orbitals in the ground electronic state of this molecule. Because these
1 2

two orbitals do not correlate directly to the two orbitals that are occupied (σ and π) in the ground state of cyclobutene, the
Woodward-Hoffmann rules suggest that this reaction, along a disrotatory path, will encounter a symmetry-imposed energy barrier.
In contrast, the excited electronic state in which one electron is promoted from π to π (as, for example, in a photochemical
2 3

excitation experiment) does correlate directly to the lowest energy excited state of the cyclobutene product molecule, which has
one electron in its p orbital and one in its p* orbital. Therefore, these same rules suggest that photo-exciting butadiene in the
particular way in which the excitation promotes one electron from π to π will produce a chemical reaction to generate
2 3

cyclobutene.

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