Symmetry and group theory

‹ The symmetry of molecules and solids is a very powerful tool for

developing an understanding of bonding and physical properties
– Used to predict the nature of molecular orbitals
– Used to predict if electronic and vibration spectroscopic transitions can be
observed
‹ We will cover the following material:
– Identification/classification of symmetry elements and symmetry operations
– Assignment of point groups
» The point group of a molecule uniquely and fully describes the molecules symmetry
– Identifying polarity and chirality using point groups
– Introduction to what a “Character Table” is
– Assigning symmetry labels to “Symmetry adapted linear combination or
orbitals”
– Assigning symmetry labels to of vibration modes
– Determining the IR and Raman activity of vibrational modes

What is symmetry?
‹ An object displays symmetry if
you can “do something to it”
(rotate it, reflect it, invert it etc.)
without changing its appearance
‹ The process of doing the
rotation, reflection etc. is
referred to as a SYMMETRY
OPERATION if it does not
change the appearance of the
molecule

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Symmetry elements
‹ A symmetry element is the line about which a rotation occurs or the
plane through which a reflection takes place etc.
‹ Symmetry elements are labeled
– Rotation axis, Cn
» The n indicates the angle through which the rotation takes place. Angle = 360/n
– Mirror plane, σh, σv, σd
» n, v or d indicate orientation of plane with respect to any rotation axes that may
be present
– Inversion center, i
– Improper rotation axis, Sn
» This involves a combination of rotation and reflection. The n indicates the angle
through which the rotation takes place. Angle = 360/n
– Identity, E
» E is always a symmetry element as doing nothing to an object always leaves it
looking just the same as it originally did.

Mirror planes
Borazine σv

σv includes the
principle rotation
axis σh

σh is perpendicular
to the principle
rotation axis

σd includes the
principle rotation
axis, but lies
between C2 axes
that are
perpendicular to the
principle axis

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Rotation axes

Rotation axes examples 1

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Rotation axes examples 2

Inversion center

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Note inversion (i) and C2 are not
equivalent

Inversion center examples

Note (a) and (b) do not

have inversion centers

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Improper rotation axes
‹ An improper rotation involves a combination of
rotation and reflection
– The rotation and the reflection do not have to be
symmetry operations of the molecule in their own right

Improper rotation axes

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S1 and S2 operations

‹ S1 is equivalent to σ
‹ S2 is equivalent to i

What symmetry elements do you have?

Cl Cl Cl
F B
Br C Br Pt Cl
Cl Cl Cl Cl

Cl Cl Br
Cl Pt Cl C C
Br Cl
Cl

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Chirality and polarity
‹ For a molecule to be chiral it must not have
a Sn symmetry element
– this includes mirror planes (S1) and inversion
centers (S2)
‹ For a molecule to be polar it must not have
an inversion center or more than one
rotation axis or a mirror plane that does not
include the principle rotation axis

Point groups
‹ The full set of point symmetry operations
that a particular molecule has is called a
point group (group of symmetry operations)
‹ There are symbols for each of the possible
point groups
‹ These symbols are often used to describe
the symmetry of a molecule
‹ Rather than saying water is bent, you can
say that water has C2v point symmetry

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Assignment of point groups
‹ Look for symmetry elements of molecule
– highest order rotation axis is usually most
important for assigning point group
‹ Point group may be obvious if the molecule
has very low symmetry or very high
symmetry
‹ Otherwise use systematic method

Point group flow chart

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Icosohedra

‹ The icosohedral point

group Ih has 5 fold
symmetry

Examples 1

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Examples 2

Examples 3

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Classifying functions by symmetry
‹ Itis possible to classify functions according to
how they behave when the symmetry
operations of a point group are performed upon
them
– for example, what happens to the 2pz orbital in
ammonia when the symmetry operations for
ammonia’s point group (C3v) are applied to the
orbital
– the behavior of a function when the symmetry
operations are applied to it is called its character

Character tables
‹ All possible sets of
characters
(irreducible
representations) for
a given point group
are shown in a
character table

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Irreducible representations
‹ There are only a certain number of distinct
ways in which a function can behave when
subjected to the symmetry operations of a
particular point group
– each of these possibilities is called an irreducible
representation
– the character of each possible irreducible
representation is listed in the character table for
that point group

Water
‹ Consider how the following orbitals behave
when subjected to the symmetry operations
of the point group C2v
– O 2s, O 2px 2pz and 2py
– H1s + H2s and H1s - H2s

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Symmetry elements for H2O

Transformation of H1s orbitals in H2O

‹ We can classify the combinations 1s(A) + 1s(B) and 1s(A) -
1s(B) by how they transform when the symmetry operations of
the point group for the molecule (C2v) are applied

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 Transformation of Opz orbital in H2O

Transformation of the other O orbitals in H2O

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MO diagram for H2O

Symmetry adapted linear combinations

‹ In molecules like H2O, NH3, CH4 where more than
one atom is symmetry equivalent, combinations of
the symmetry equivalent orbitals transform
according to a irreducible representations of the
molecules point group
– These combinations of orbitals are referred to as SALCS
(Symmetry Adapted Linear Combinations).
‹ These combinations can be calculated using group
theory
– However, for this class we will just show which
combinations are appropriate for each point group

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SALCS – 2 and 3 fold symm

SALCS – 4 and 5 fold symm

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SALCS – 6 fold symm

SALCS – oct and tet symm

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 SALCS for NH3
Transforms as A1

Transform as E

Symmetry of N orbitals in NH3

‹ The N 2pz orbital and
the N 2s orbital
transform as A1 in the
point group C3v
‹ N 2px and 2py
transform as E

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MO diagram for NH3
‹ dsd

IR and Raman spectroscopy

‹ In IR spectroscopy a photon is
completely absorbed to excite a
molecular vibration
‹ In Raman spectroscopy quite
high energy photons are used
and some energy is lost from
the photon to excite a vibration.
The intensities and energies of
the photons that have lost
energy to excite the vibration
are measured in order to get a
spectrum

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Raman spectroscopy
‹ Laser excitation source is used. Intensity of
inelastically scattered photons is measured

Vibrational spectroscopy and symmetry

‹ For molecules with some symmetry, group theory can be
used to predict how many vibrational modes should appear in
the infrared and Raman vibrational spectra of the molecule
– Not all modes are both IR and Raman active
» For centrosymmetric molecules anything that is IR active is not Raman
active an visa versa
– However, in neutron vibrational spectroscopy all modes can be
observed although modes involving H motion tend to give the
strongest signals
‹ As different molecular symmetries lead to different numbers
of IR and Raman active bands this is a useful approach for
determining the shape (symmetry) of molecules where there
is a possible ambiguity
– Often used in matrix isolation studies where some very reactive
species has been trapped in a noble gas solid at low T and there are no
easy alternative ways of determining symmetry
– Useful for establishing which isomer you are looking at. For example,
cis and trans isomers will typically give different vibrational modes
because the molecules have different symmetries

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Why does symmetry mater?
‹ For a transition involving the absorption of a photon (IR, optical etc.)
there must be a change in dipole moment on going from the ground
to the excited state. This occurs when the following integral has a
none zero value:

∫ψ 1µψ 2 dτ
Ψ1 and ψ2 are the ground and excited state
wavefunctions, µ is the dipole moment operator and
the integral is over all space

This integral can only be none zero if the function being integrated has a
component with symmetry like that of the highest symmetry irreducible
representation of the molecules point group

As µ transforms like the functions x, y and z, this in practice means that you only
observe an IR transition when the excited state wavefunction belongs to the same
irreducible representation as either x, y or z. So we need to be able to determine the
symmetry properties of the vibrationally excited state to predict if we will see a transition
to it.

Raman transitions
‹ Raman excitation occurs only when there is a change in polarizability
on going from the ground to the excited state. This occurs when the
following integral has a none zero value:

∫ψ 1αψ 2 dτ
Ψ1 and ψ2 are the ground and excited state
wavefunctions, α is the operator for polarizability and
the integral is over all space

As α transforms like the functions x2, y2, z2, xy, xz etc. this in practice means that
you only observe a Raman transition when the excited state wavefunction belongs
to the same irreducible representation as either x2, y2, z2, xy, xz etc. So we need to
be able to determine the symmetry properties of the vibrationally excited state to
predict if we will see a transition to it.

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Examples of vibrational selection rules
A1, B1 and B2 symmetry
vibrations will be IR active.
A1, A2, B1 and B2 symmetry
vibrations will be Raman active.

A1 and E symmetry vibrations

will be IR active.
A1, and E symmetry vibrations
will be Raman active.

A1, and E symmetry vibrations

will be IR active.
A1, B1, B2 and E symmetry
vibrations will be Raman active.

How many vibrational modes?

‹ For a molecule with N atoms there
are a total of 3N degrees of freedom
(x, y and z coordinates for each
atom)
– Three of these degrees of freedom are
used to describe the position of the
molecules center of mass
– Three are used in determining the
orientation of the molecule in space
(assuming it is non-linear)
– The remaining 3N-6 degrees of freedom
correspond to distinct vibrational modes
of the molecule (stretching and bending)

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 Determining the symmetry of
stretching modes
‹ Symmetry for a normal (vibrational) mode
can be determined by group theoretical C2V E C2 σv(xz) σv(yz)
analysis χsymm 1 1 1 1 A1
‹ Consider what happens to the displacement
vectors for each mode when you apply the χanti 1 -1 -1 1 B2
symmetry operations of the point group

Both IR
C2v active

y
Only B2u
IR active

D2h
A1g is Raman x
active

D2h E C2(z) C2(y) C2(x) i σ(xy) σ(xz) σ(yz)

χsymm 1 1 1 1 1 1 1 1 A1g
χanti 1 -1 1 -1 -1 1 -1 1 B2u

Vibrational spectra for Pd(NH3)2Cl2

Only one IR active

Pd-Cl stretch

Two IR active Pd-Cl

stretches

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