INORGANIC CHEMISTRY 2

UNIT 2. INTRODUCTION TO GROUP

THEORY & SYMMETRY

LECTURER: NORGERIS ALVAREZ LOPEZ

 TOPIC : GROUP THEORY AND
SYMMETRY
INSTRUCTIONAL OBJECTIVES:
1. Discuss the terms group theory and symmetry.
a. Term symmetry and group theory in terms of mathematical concepts.
b. Point groups and different types of operation, using diagrams, these
operations may include: n-fold rotation, n-fold improper rotation,
reflection, inversion and Identity, E
 POINT GROUP
• A Point Group describes all the symmetry operations that can be performed on a
molecule that result in a conformation indistinguishable from the original.
• Point groups are used in Group Theory, the mathematical analysis of groups, to
determine properties such as a molecule's molecular orbitals.

ASSIGNING POINT GROUPS

• While a point group contains all of the symmetry operations that can be performed
on a given molecule, it is not necessary to identify all of these operations to
determine the molecule's overall point group.
• A molecule's point group can be determined by following a set of steps which
analyze the presence (or absence) of particular symmetry elements.
Quantum Chemistry 12.5 - Point Groups https://youtu.be/cbxKulVtWbU
 SYMMETRY ELEMETS
The symmetry elements that a molecule may possess are:
• E - the identity. The identity operation consists of doing nothing, and the corresponding
symmetry element is the entire molecule. Every molecule has at least this element.
• Cn - an n -fold axis of rotation. Rotation by 360°/n leaves the molecule unchanged.
• σ - a plane of symmetry. Reflection in the plane leaves the molecule looking the same.
In a molecule that also has an axis of symmetry, a mirror plane that includes the axis is
called a vertical mirror plane(σv) , while one perpendicular to the axis is called a
horizontal mirror plane (σh) . A vertical mirror plane that bisects the angle between two
C2 axes is called a dihedral mirror plane (σd)
• i - a center of symmetry. Inversion through the center of symmetry leaves the molecule
unchanged. Inversion consists of passing each point through the center of inversion and
out to the same distance on the other side of the molecule.
• Sn - an n-fold improper rotation axis (also called a rotary-reflection axis). The rotary
reflection operation consists of rotating through an angle 360°/n about the axis,
followed by reflecting in a plane perpendicular to the axis.
 STEPS FOR ASSIGNING A MOLECULE'S POINT GROUP
1. Determine if the molecule is of high or low symmetry.
2. If not, find the highest order rotation axis, Cn.
3. Determine if the molecule has any C2 axes perpendicular to the principal Cn axis. If
so, then there are n such C2 axes, and the molecule is in the D set of point groups.
If not, it is in either the C or S set of point groups.
4. Determine if the molecule has a horizontal mirror plane (σh) perpendicular to the
principal Cn axis. If so, the molecule is either in the Cnh or Dnh set of point groups.
5. Determine if the molecule has a vertical mirror plane (σv) containing the principal
Cn axis. If so, the molecule is either in the Cnv or Dnd set of point groups. If not, and
if the molecule has n perpendicular C2 axes, then it is part of the Dn set of point
groups.
6. Determine if there is an improper rotation axis, S2n, collinear with the principal Cn
axis. If so, the molecule is in the S2n point group. If not, the molecule is in the Cn
point group.
Quantum Chemistry 12.7 - Determining Point Groups https://youtu.be/KiQjvUcBVMw
DECISION TREE FOR DETERMINING A MOLECULE'S POINT GROUP
 LOW SYMMETRY POINT GROUPS

Low symmetry point groups include the C1, Cs, and Ci groups

Low Symmetry Groups (Non-rotational Groups)

Group Description Example

C1 only the identity operation (E) CHClBrF
Cs only the identity operation (E) and one mirror plane C2H2ClBr
Ci only the identity operation (E) and a center of inversion (i) C2H2Cl2Br2
 LOW SYMMETRY POINT GROUPS
(only E or E+ 1 other symmetry)

C1 - contains only the identity CS - contains the identity E Ci - contains the identity E and a
(a C1 rotation is a rotation and a plane of center of inversion i.
by 360° and is the same reflection σ.
as the identity operation
E) e.g. CHBrFCl.
E, σ E, i
Chiral
E
 HIGH SYMMETRY POINT GROUPS

High symmetry point groups include the Td, Oh, Ih, C∞v, and D∞h groups.

Group Description Example

C∞v linear molecule with an infinite number of rotation axes and vertical mirror planes (σv) HBr
D∞h linear molecule with an infinite number of rotation axes, vertical mirror planes (σv), CO2
perpendicular C2 axes, a horizontal mirror plane (σh), and an inversion center (i)
Td typically have tetrahedral geometry, with 4 C4 axes, 3 C2 axes, 3 S4 axes, and 6 dihedral CH4
mirror planes (σd)
Oh typically have octahedral geometry, with 3 C4 axes, 4 C3 axes, and an inversion center SF6
(i) as characteristic symmetry operations
Ih typically have an icosahedral structure, with 6 C5 axes as characteristic symmetry B12H122-
operations
 HIGH SYMMETRY POINT GROUPS
C∞v D∞h
Linear molecule with an infinite number Linear molecule with an infinite number of
of rotation axes(C∞) and vertical mirror planes rotation axes, vertical mirror planes (σv),
(∞σv) perpendicular C2 axes, a horizontal mirror plane (σh),
and an inversion center (i)

Dinitrogen monoxide
Hydrogen fluoride Carbon dioxide
Oxygen (and
(and all other
all other
heteronuclear
homonuclear
diatomic
diatomic
molecules)
Hydrogen cyanide molecules)
Ethyne
E 2C∞ ∞σv E 2C∞ ∞σv i 2S∞ ∞C2

Td
Typically have tetrahedral
geometry, with 4 C4 axes, 3 C2
axes, 3 S4 axes, and 6 dihedral
mirror planes (σd)
Methane
E 8C3 3C2 6S4 6σd
HIGH SYMMETRY POINT GROUPS
Oh
Typically have octahedral geometry, with
3 C4 axes, 4 C3 axes, and an inversion
center (i) as characteristic symmetry
operations
Sulfur hexafluoride
E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd
Ih
Typically have an icosahedral
structure, with 6 C5 axes as
characteristic symmetry
operations
Buckminsterfullerene
E 12C5 12C52 20C3 15C2 i
12S10 12S103 20S6 15σ
 C groups
C groups (Single axis groups, only one rotation)
• The C set of point groups are classified as Cnh, Cnv, or Cn, where n refers to the
principal axis of rotation.
• The C set of groups are characterized by the absence of nC2 axes perpendicular to
the principal Cn axis.
• Further classification of a molecule in the C groups depends on the presence of
horizontal or vertical/dihedral mirror planes.
Group Description Example
horizontal mirror plane (σh) perpendicular to the
Cnh boric acid, H3BO3 is C3h
principal Cn axis
Cnv vertical mirror plane (σv) containing the principal Cn axis ammonia, NH3 is C3v
Cn no mirror planes P(C6H5)3 is C3
 C groups Cnh

Identity, horizontal mirror plane (σh) perpendicular to the principal Cn axis

C2h C3h
Planar with inversion center Propeller

Trans-1,2-dichloroethylene Trans-dinitrogen difluoride Boric acid

E C2 i σh E C3 C32 σh S3 S3-1
 C groups Cnv
Contains the identity, an n-fold axis of rotation, and n vertical mirror planes σv

C2v C3v C4v

Bent or see-saw Trigonal pyramidal Square pyramidal
or tetrahedral

Water Ammonia Phosphorus Xenon

Sulfur tetrafluoride
oxychloride oxytetrafluoride

E C2 σv(xz) σv‘(yz) E 2C3 3σv E 2C4 C2 2σv 2σd

 C groups Cn
• Contains the identity and an n-fold axis of rotation.
• No mirror planes
C3
C2
"Open book geometry," chiral Propeller, chiral

Hydrogen peroxide Hydrazine Triphenylphosphine Phosphoric acid

E C2 E C3 C32
A chiral objects are superimposable with their mirror images.
 D group
D groups- ( Dihedral groups, has nC2 axes perp. to principal axis)

• The D set of point groups are classified as Dnh, Dnd, or Dn, where n refers to the
principal axis of rotation.
• Overall, the D groups are characterized by the presence of n C2 axes perpendicular to
the principal Cn axis.
• Further classification of a molecule in the D groups depends on the presence of
horizontal or vertical/dihedral mirror planes.

Group Description Example

Dnh n perpendicular C2 axes, and a horizontal mirror plane (σh) Benzene, C6H6 is D6h
Dnd n perpendicular C2 axes, and a vertical mirror plane (σv) Propadiene, C3H4 is D2d
Dn n perpendicular C2 axes, no mirror planes [Co(en)3]3+ is D3
 D group Dnd
Dnd - contains the same symmetry elements as Dn with the addition of n dihedral mirror
planes.

D2d D3d D4d

90° twist 60° twist 45° twist

Ethane Sulfur (crown

Allene (staggered rotamer) conformation of S8)

E 2C3 3C2 i 2S6 3σd E 2S8 2C4 2S83 C2 4C2' 4σd

E 2S4 C2 2C2' 2σd
 D group Dnh
Dnh - contains the identity, an n perpendicular C2 axes, and a horizontal mirror plane σh

D2h D3h D4h D5h D6h

Trigonal planar or Square planar Pentagonal Hexagonal
Planar with
trigonal bipyramidal
inversion center

Xenon Cyclopentadienyl Benzene

Ethylene Boron Phosphorus
trifluoride pentachloride tetrafluoride anion
E C2(z) C2(y) C2(x) i E 2C4 C2 2C2' E 2C5 2C52 E 2C6 2C3 C2
E C3 3C2 σh 2S3 3σv 5C2' σh 2S5
σ(xy) σ(xz) σ(yz) 2C2'' i 2S4 σh 3C2' 3C2‘’ i 2S3
2σv 2σd 2S53 5σv 2S6 σh 3σd 3σv
 D group Dn
Dn - contains the identity, an n-fold axis of rotation, and n 2-fold rotations about axes
perpendicular to the principal axis.
D2 D3
Twist, chiral Triple helix, chiral

Biphenyl
Tris(ethylenediamine)cobalt(III) cation
(skew conformation)

E 2C3 3C2'
E C2(x) C2(y) C2(z)
 S Groups
• The S set of point groups are classified as S2n, where n refers to the principal axis of
rotation.
• The S set of groups are characterized by the absence of n C2 axes perpendicular to the
principal Cn axis, as well as the absence of horizontal and vertical/dihedral mirror
planes.
• There is an improper rotation (or a rotation-reflection) axis collinear with the principal
Cn axis.

Group Description Example

improper rotation (or a rotation-reflection)
S4 12-crown-4 is S4
axis collinear with the principal Cn axis

E S4 C2 S43
Quantum Chemistry 12.6 - Point Group Examples https://youtu.be/DINEG-MvVps
References

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(P
hysical_and_Theoretical_Chemistry)/Chemical_Bonding/Molecular_Orbital_Theory/How_to_Build_Molecular_Orbitals

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Book%3A_Symmetry_(Va
llance)/02._Symmetry_operations_and_symmetry_elements

https://en.wikibooks.org/wiki/Advanced_Inorganic_Chemistry/Molecular_Point_Group

https://www.youtube.com/watch?v=elSoLFTACwo

https://www.youtube.com/watch?v=a9G1bLCEhko

https://www.slideshare.net/shobana3/group-theory-symmetry

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Book%3A_Symmetry_(
Vallance)/01%3A_Chapters/1.07%3A_Mathematical_Definition_of_a_Group
 MATHEMATICAL DEFINITION OF A GROUP

A mathematical group is defined as a set of elements ( g1 , g2 , g3 ...) together with a

rule for forming combinations gi gj . The number of elements h is called the order of
the group.

The elements are the symmetry operations of a molecule and the rule for combining
them is the sequential application of symmetry operations investigated in the previous
section. The elements of the group and the rule for combining them must satisfy the
following criteria.
 MATHEMATICAL DEFINITION OF A GROUP

1. The group must include the identity E , for which

for all the elements of the group.
2. The elements must satisfy the group property that the combination of any pair of
elements is also an element of the group.
3. Each element gi must have an inverse gi−1 , which is also an element of the group,
such that
(e.g. in C3v the inverse of C3+ is C3− , the inverse of (σv is σv', the inverse gi−1
effectively 'undoes’ the effect of the symmetry operation gi).
4. The rule of combination must be associative i.e.

The above definition does not require the elements to commute, which would require
 MATHEMATICAL DEFINITION OF A GROUP
• As we discovered in the C3v example above, in many groups the outcome of consecutive application of
two symmetry operations depends on the order in which the operations are applied. Groups for which
the elements do not commute are called non-Abelian groups; those for which they elements do
commute are Abelian.

• Group theory is an important area in mathematics, and luckily for chemists the mathematicians have
already done most of the work for us. Along with the formal definition of a group comes a
comprehensive mathematical framework that allows us to carry out a rigorous treatment of symmetry
in molecular systems and learn about its consequences.

• Many problems involving operators or operations (such as those found in quantum mechanics or group
theory) may be reformulated in terms of matrices. Any of you who have come across transformation
matrices before will know that symmetry operations such as rotations and reflections may be
represented by matrices. It turns out that the set of matrices representing the symmetry operations in
a group obey all the conditions laid out above in the mathematical definition of a group, and using
matrix representations of symmetry operations simplifies carrying out calculations in group theory.
Before we learn how to use matrices in group theory, it will probably be helpful to review some basic
definitions and properties of matrices.