1-Introduction to Molecular Spectroscopy

COURSE NAME: MOLECULAR SPECTROSCOPY

COURSE CODE: 4024577-2
 Recall the following:
• Matter exhibits both particle-like and wave-like properties
• Matter on the molecular scale exhibits quantum behavior
– A molecule will only rotate or vibrate at certain rates (i.e.,
discrete energies)
• For each energy levels are separated by gaps (quantized).
• If a photon of light strikes the molecule with the exact amount of
energy needed, a molecule absorbs this photon.
• Energy is eventually released from the molecule generally in the
form of heat
• Spectroscopy involves an interaction between matter and light
(EMR)
 Spectroscopy
• The analysis of the EM radiations emitted, absorbed or scattered
by atoms, molecules or matter
• Photons of the radiation bring information to us about the atom,
molecule or matter.
• The difference between molecular and atomic spectroscopy: a
molecule can make a transition between its electronic, rotational
and vibrational states.
• The rotational and vibrational spectroscopy of a molecule can
provide information about the bond lengths, bond angles and
bond strength in the molecule.
Electromagnetic spectrum
 Nature of electromagnetic (EM)
radiation

– Electric component (E).

It has the form of oscillating electric field.
– Magnetic component (H).
It has the form of oscillating magnetic field.

5
 Elementary Molecular Spectroscopy

E2

E=h

E1
Absorption emission

Quantum mechanics dictates that virtually all energy

transitions are discrete:
• Absorption: molecule increases its energy

• Emission: molecule decreases its energy.

Molecules can store energy in 4 discrete ways:

1.Translational (kinetic) energy – directly associated with the the

TEMPERATURE of the gas.
2.Vibrational : Most molecules are constantly vibrating! (if their
structures allow it)
3.Rotational: Molecules can rotate on top of vibrating.
4.Electronic: Relates to energy states of electrons inside a
molecule

Energy storage potential in each type is :

A.Electronic : HIGH (associated with visible/UV)
B.Vibrational: MEDIUM-LOW (associated with IR/Microwave)
C.Rotational: quite low – tacked on as a modified to vibrations,
leading to “vibrational-rotational” absorption features.
The types of interactions that occur
in matter depend on the rate of
oscillations that must be induced
(i.e the wavelength of the incident
radiation).

On the whole, shorter wavelength,

radiation interacts with lighter and
smaller parts of matter whereas more
sluggish slower oscillating radiation
affects the larger parts of matter.

We are mainly concerned with

mechanisms affecting electrons,
and atoms to more bulky molecules
- mostly vibrational and rotational
spectra
 *

*Induced through vibrations

THE OVERALL PICTURE
From the Previous information, the aim of the coming lectures will
be how to deal with the absorption by molecules for different
regions of the electromagnetic radiation and try to answer the
following:

•How do molecules absorb radiation?

•Why do only certain molecules absorb radiation?

• What dictates the nature of the absorption (wavelength,

strength)?
 Rotational Spectroscopy

COURSE NAME: Molecular Spectroscopy

COURSE CODE:4024577-2
Incident electromagnetic waves can excite the rotational levels of molecules
provided they have an electric dipole moment. The electromagnetic field
exerts a torque on the molecule.
The spectra for rotational transitions of molecules is typically in
the microwave region of the electromagnetic spectrum.

❖ Absorption of microwave radiation causes heating due to increased molecular

rotational activity....
 Absorption of Electromagnetic Radiation - The Coupling Mechanism

An electromagnetic wave is an oscillating electrical field and interacts only with molecules that
can undergo a change in dipole moment.

The oscillating dipole can be provided by the rotation of a permanent dipole like for example
HCl. This type of interaction leads to microwave spectra

H−Cl

Fig. The rotation of a polar diatomic molecule, showing the fluctuation in the dipole moment
measured in a particular direction
 Microwave Spectroscopy
Incident electromagnetic waves can excite the rotational levels of molecules provided they
have an electric dipole moment. The electromagnetic field exerts a torque on the molecule.

❖ Homonuclear diatomic molecules (such as H2, O2, N2 , Cl2) – have zero dipole (non
polar) -- have zero change of dipole during the rotation – hence NO interaction with
radiation -- hence homonuclear diatomic molecules are microwave inactive

❖ Heteronuclear diatomic molecules (such as HCl, HF, CO) – have permanent

dipolemoment (polar compound) -- change of dipole occurs during the rotation –
hence interaction with radiation takes place – Therefore, heteronuclear diatomic
molecules are microwave active.
 RIGID ROTOR
For simplicity, we can consider only rotational motion of rigid diatomic molecule,

A diatomic molecule can rotate around a

vertical axis. The rotational energy is
quantized.

Assume a rigid (not elastic) bond

r0 = r1 + r2
For rotation about center of gravity,
C:
0
m1r1 = m2r2
= m2 (r0 - r1)

m2r0 m1r0
r1 = r2 =
m1 + m2 m1 + m2
 RIGID ROTOR
Moment of inertia about C:
IC = m1r12 + m2r22 = m2r2r1 + m1r1r2 = r1r2 (m1 + m2)

m1m2 2 1 1 1
I= r0 = μr0
2
 = reduced mass, = +
m1 + m2 μ m1 m2

A diatomic molecule can rotate around a vertical axis. The rotational energy is quantized. By the
using Schrödinger equation, the rotational energy levels allowed to the rigid diatomic molecule are
given by,

J = Rotational quantum number (J = 0, 1, 2, …)

I = Moment of inertia = mr2
 = reduced mass = m1m2 / (m1 + m2)
r = internuclear distance
 Energy is quantized

Planck suggests that radiation (light, energy) can

only come in quantized packets that are of size hν.

E = h
Planck’s constant
h = 6.626 × 10-34 J·s
Energy (J)
Planck, 1900
Frequency (s-1)
Note that we can specify the energy by specifying any one of the following:

1. The frequency, n (units: Hz or s-1): E = h

2. The wavelength, λ, (units: m or cm or mm): hc

 =
E=
Recall: c 

3. The wavenumber,
~ (units: cm-1 or m-1)
1 E = hc~
Recall: ~ =

 Rotational Spectra of Rigid Diatomic molecule

Rotational Energy Levels for rigid rotor:

Where
 Rotational Spectra of Rigid Diatomic molecule
For rigid rotor, J → J + 1,

The allowed rotational energy Allowed transitions between the energy levels
levels of a rigid diatomic molecule of a rigid diatomic molecule and the spectrum
 Rotational Spectra of Rigid Rotor
Selection Rule: Apart from Specific rule, J=  Gross rule- the molecule
should have a permanent electric dipole moment,  . Thus, homonuclear
diatomic molecules do not have a pure rotational spectrum. Heteronuclear
diatomic molecules do have rotational spectra.

j = 1
j = +1 (absorption)
j = −1 (emission)
Rotational Energy levels
 The rotation spectrum of 12C16O at 40 K.

The lines are nearly equally spaced and vary in intensity.

We also will learn why the lines are nearly equally spaced and vary in intensity.
Such spectra can be used to determine bond lengths, and even bond angles in
polyatomic molecules.
 Vibrational spectroscopy

COURSE NAME:Molecular Spectroscopy

COURSE CODE: 4024577-2
 Hook’s Law

Hook’s Law,

F=-kx
F is the restoring force
x is the displacement from equilibrium
k is the force constant

The restoring force proportional to the displacement of particle from its equilibrium
position and the force constant k of the spring.
Vibrational spectra: Harmonic oscillator model
The Simple Harmonic Oscillator Model: H2 molecule

H1 H2’
In this case, energy curve
E2 H2”
is parabolic,
1
E = 2 k (r – req)2
E1 H2”
H1 H 2’

req
 Harmonic Oscillator Model
The Simple Harmonic Oscillator Model: H2 molecule

The compression & extension of a bond (like

a spring) obeys Hooke’s Law,
H1 H 2’
E2 H2”

f is the restoring force

E1 H2” k is the force constant
H1 H 2’

In this case, energy curve is

req parabolic,

1
E= k (r – req)2
2
 Anharmonic Oscillator Model

Where a is a constant for a particular

molecule and Deq is the dissociation energy.

The Morse potential (blue) and harmonic oscillator potential (green). The
potential at infinite internuclear distance is the dissociation energy for pure
vibrational spectra.
 Vibrational spectra: Harmonic oscillator model

Oscillation Frequency,

k is the force constant

 = reduced mass,

Vibrational frequency only dependent on the mass of

the system and the force constant .

From Schrodinger equation, Vibrational energies for simple harmonic oscillator,

 Vibrational spectra: Harmonic oscillator model

At

Zero-point energy
The implication is that the diatomic molecule
(and, indeed, any molecule) can never have
zero vibrational energy; the atoms can never
be completely at rest relative to each other.

The simple selection rule for the harmonic oscillator

undergoing vibrational changes

The allowed vibrational energy levels and transitions between them for a diatomic molecule
undergoing simple harmonic motion.
 Vibrational spectra: Harmonic oscillator model

Oscillation Frequency,

k is the force constant

 = reduced mass,

The vibrational frequency is increasing with:

❖ increasing force constant k ( = increasing bond strength)
❖ decreasing atomic mass

• Example: k cc > k c=c > k c-c

 Infrared Spectroscopy

POSITION REDUCED MASS LIGHT ATOMS

HIGH FREQUENCY

BOND STRENGTH STRONG BONDS

(STIFFNESS) HIGH FREQUENCY

The vibrational frequency is increasing with:

• increasing force constant k (= increasing bond strength)
• decreasing atomic mass
 Molecular vibrations

❑ How many vibrations are possible (= fundamental vibrations)?

A molecule has as many degrees of freedom as the total degree of freedom

of its individual atoms.
Each atom has three degrees of freedom (corresponding to the Cartesian
coordinates), thus in an N-atom molecule there will be 3N degree of
freedom.
In molecules, movements of the atoms are constrained by interactions
through chemical bonds.
 Molecular vibrations
Translation - the movement of the entire molecule while the positions of the
atoms relative to each other remain fixed: 3 degrees of translational freedom.
Rotational transitions – interatomic distances remain constant but the entire
molecule rotates with respect to three mutually perpendicular axes: 3 rotational
freedom (nonlinear), 2 rotational freedom (linear).
Fundamental Vibrations
Vibrations – relative positions of the atoms change while the average position
and orientation of the molecule remain fixed.
Molecular vibrations
 Stretching and Bending

Types of Molecular Vibrations: Vibrations fall into the basic categories

of stretching and bending.

❑ Stretching vibration involves a continuous change in the inter-atomic

distance along the axis of the bond between two atoms.

❑ Bending vibrations are characterized by a change in the angle between

two bonds and are of four types: scissoring, rocking, wagging, and
twisting.
Stretching Vibration
Bending Vibration
 H2O: Stretching and Bending Vibrations

❑ Bending is easier than stretching -- happens at lower energy (lower

wavenumber)
❑ Bond Order is reflected in ordering -- triple > double > single (energy)
with single bonds easier than double easier than triple bonds
❑ Heavier atoms move slower than lighter ones
Examples of Vibrational Modes
Example 1: Consider Water
Examples of Vibrational Modes
Example 1: Consider Water

Vibrations of water
Gas v1, cm-1 v2, cm-1 v3, cm-1
H216O 3657.1 1594.7 3755.9

3756 cm-1 3657 cm-1 1595 cm-1

Examples of Vibrational Modes
Example 2: Consider Carbon Dioxide
 Selection Rules

❑ A molecule will absorb infrared radiation if the change in vibrational

states is associated with a change in the dipole moment () of the
molecule.

❑ Vibrations which do not change the dipole moment are Infrared

Inactive (homonuclear diatomics).

Homonuclear diatomic molecules (O2, N2, H2, Cl2) – IR

Inactive

Heteronuclear diatomic molecules (HF, HCl) – IR Active

Dipole moment is greater when electronegativity difference between the

atoms in a bond is greater.
Some electronegativity values are:
H 2.2; C 2.55; N 3.04; O 3.44; F 3.98; P 2.19; S 2.58; Cl 3.16
 Infrared Spectrum of Carbon Dioxide (CO2)

Stretching

Bending
 Symmetric Stretching Vibration of the CO2
To be "active" means that absorption of a photon to excite the vibration
is allowed by the rules of quantum mechanics.

[Aside: the infrared "selection rule" states that for a particular vibrational mode
to be observed (active) in the infrared spectrum, the mode must involve a
change in the dipole moment of the molecule.]

The symmetric stretch is not infrared active, and so this vibration is not
observed in the infrared spectrum of CO2.
 Electronic Spectroscopy

COURSE NAME:Molecular Spectroscopy

COURSE CODE: 4024577-2
•The Energy of Electronic Transitions

• Electronic excitations are responsible for

giving color to the objects we observe.
• UV-visible spectroscopy provides a very
useful qualitative tool for identifying
molecules and determine energy levels in
molecules.
•Molecular Term Symbols

• In electronic excitations, molecular term

describe the electronic states of molecules.
• L and S (ML and MS) is chosen to be the z
axis, and S nare to specify individual
n
states in
diatomic  mli and M S =  msi
M L =molecules.
i =1 i =1

where mli, mls = z components of orbital and spin angular

momentum for the i th electron in its
molecular orbital.
Example:
What is the molecular term symbol for the H2 molecule
in its ground state?

In the ground state, the H2 molecule is described by

the (1σg)2 configuration. For both electrons, ml=0.
Therefore, Λ=0, and we are dealing with a Σ term.
Because of the Pauli principle, one electron has
ms=+1/2 and the other has ms=-1/2.

Therefore, MS=0 and it follows that S=0. It remains to be

determined whether the MO has g or u symmetry. Each term
in the antisymmetrized MO is of the form σg x σg. Recall
that the products of two even or odd functions is even,
and the product of an odd and an even function is
odd.
•Therefore, the product of two g (or two u) functions is
a g function, and the ground state of the H2 molecule
is 1Σg
Transitions Between Electronic States of Diatomic
Molecules
• Diatomic molecules have spacing between the
various rotational-vibrational-electronic states which
is large to allow individual states to be resolved.

• Each of the molecular bound

states of O2 has well-defined
vibrational and rotational
energy levels.
The Vibrational Fine Structure of Electronic Transitions
in Diatomic Molecules:

• Vibrational and rotational quantum numbers can

change during electronic excitation.
• Born-Oppenheimer approximation can be
used to determine vibrational transition between
electronic electronic
states.
 (r1 ,..., rn , R1 ,..., Rm ) =  (r ,..., r , R
1
fixed
n
fixed
1 ) 
vibrational
,..., Rm (R1 ,..., Rm )

where R1,…,Rm depends on position of the nuclei

r1,…rn depends on the position of electrons
•Franck-Condon principle

• Franck-Condon principle states that transitions

between electronic states correspond to vertical
lines on an energy versus inter-nuclear distance
diagram.

• Electronic transitions occur on a

timescale that is very short
compared to the vibrational
period of a molecule
•UV-Visible Light Absorption in Polyatomic Molecules

• Rotational and vibrational transitions are

possible if an electronic transition occurs in
polyatomic molecules.
• The concept of chromophores is useful for
electronic spectroscopy of polyatomic
molecules.
• A chromophore is a chemical entity
embedded within a molecule that absorbs
radiation at the same wavelength in different
molecules.
• The intensity of absorption for (a) an atom, (b) a
diatomic molecule, and (c) a polyatomic
molecule.
• The energy difference between the initial and
final states determines the frequency of the
spectral line.
• The energy increases in the sequence n➔π*, π➔
π*, and σ➔σ*.
• Transitions among the Ground and Excited States

• There are possible transitions among the

ground and excited electronic states.
Transitions among the Ground and
Excited States

The 2 types of transitions are:

• Radiative transitions
- photon is absorbed/emitted
• Nonradiative transitions
- energy transferred between molecule to the
surroundings
 NUCLEAR MAGNETIC
RESONANCE

COURSE NAME:Molecular Spectroscopy

COURSE CODE:4024577-2
•NMR SPECTROSCOPY
• Nuclear magnetic resonance spectroscopy has
become a very powerful tool for structure elucidation
to an organic chemist.
• This technique is based on transitions between
nuclear spin states by absorption of electromagnetic
radiations in the radiofrequency region of roughly 4
to 900 MHz by certain organic molecules when they
are placed in a strong magnetic field.
• E. Bloch and F. Purcell (1952) were awarded nobel
prize for demonstrating the NMR effect in 1946.
•Introduction to NMR Spectroscopy
• When a charged particle such as a proton spins on its axis, it
creates a magnetic field. Thus, the nucleus can be considered to
be a tiny bar magnet.
• Normally, these tiny bar magnets are randomly oriented in space.
However, in the presence of a magnetic field B0, they are oriented
with or against this applied field. More nuclei are oriented with
the applied field because this arrangement is lower in energy.
• The energy difference between these two states is very small
(<0.1 cal).

61
 The Physical Basis of the NMR Experiment

• Imagine a charge travelling circularily

about an axis builds up a magnetic
moment
• It rotates (spins) about its own axis (the
blue arrow) and precesses about the axis
of the magnetic field B (the red arrow).
The frequency of the precession () is
proportional to the strength of the
magnetic field:
  =  B0
 = magnetogyro ratio
Magnetic field mrasured in Tesla
1 T = 10,000 gauss
 •Nuclear Magnetic Resonance
• Resonance: In NMR spectroscopy, resonance is the
absorption of energy by a precessing nucleus and the
resulting “flip” of its nuclear spin from a lower energy
state to a higher energy state.
• The precessing spins induce an oscillating magnetic
field that is recorded as a signal by the instrument.
– Signal: A recording in an NMR spectrum of a nuclear
magnetic resonance.
Nuclear Magnetic Resonance
– (a) Precession and (b) after absorption of
electromagnetic radiation.
 •Larmour frequency

• Precession: The circular movement of the magnetic

moment in the presence of the applied field.
• Larmour frequency : The angular frequency of the
precessionis related to the external magnetic field
strength B0, by the gyromagnetic ratio  :
0 = B0
•Nuclear Spin in B0
– The energy difference between allowed spin states
increases linearly with applied field strength.
– Values shown here are for 1H nuclei.
E and Magnet Strength
• Energy difference is proportional to the magnetic
field strength.
• E = h =  h B0 The Larmor Equation
2
• Gyromagnetic ratio, , is a constant for each
nucleus (26,753 s-1gauss-1 for H).
•Magnetogyric ratio()

The larger the value of the magnetogyric ratio,

the larger the
Magnetic moment () of the nucleus and the
easier it is to see by NMR spectroscopy.
Energy difference (E) between Iz = +1/2 and
Iz = -1/2.
 •The Physical Basis of the NMR

• Nuclear magnetic resonance, or NMR as it is

abbreviated by scientists, is a phenomenon which
occurs when the nuclei of certain atoms are
immersed in a static strong magnetic field and
exposed to a second oscillating magnetic field in the
form of radiofrequency pulses, it is possible to
transfer energy into the spin system and change the
state of the system. After the pulse, the system
relaxes back to its state of equilibrium, sending a
weak signal that can be recorded.
 Classical View of NMR
(compared to Quantum view)
Precession or Larmor frequency:
 = 2  o =  B (radians)

angular momentum
(l)
l o 

Bo

Simply, the nuclei spins about its

axis creating a magnetic moment  Apply a large external field (Bo)
and  will precess about Bo at its
Maxwell: Magnetic field≡ Moving charge
Larmor () frequency.

Important: This is the same frequency obtained from the

energy transition between quantum states
 •Quantum-mechanical treatment:
• The dipole moment  of the nucleus is described in
quantum-mechanical terms as
=J
• Therein, J is the spin angular momentum and  the
magnetogyric ratio of the spin. When looking at single spins
we have to use a quantum-mechanical treatment.
• Therein, the z-component of the angular momentum J is
quantitized and can only take discrete values

• J is related to spin quantum number of the nuclei I

-I,…,o,…,+I
 •Spin quantum number(I)

• Nuclear spin is characterized by a spin number, I,

which can be zero or some positive integer multiple
of 1/2 (e.g. 1/2, 1, 3/2, 2 etc.). Nuclei whose spin
number, I= 0 have no magnetic moment();eg. 12C
and 16O show no NMR signal. Elements such as 1H,
13C, 19F and 31P have I=1/2, while others have even

higher spin numbers:

• I=1 14N, 2H
• I=3/2 11B, 35Cl, 37Cl, 79Br, 81Br.
• As the values for I increase, energy levels and
shapes of the magnetic fields become progressively
more and more complex.
•Nuclear Spin States
• An electron has a spin quantum number of 1/2 with allowed
values of +1/2 and -1/2.
– This spinning charge has an associated magnetic field.
– In effect, an electron behaves as if it is a tiny bar magnet and has what
is called a magnetic moment.
• The same effect holds for certain atomic nuclei.
– Any atomic nucleus that has an odd mass number, an odd atomic
number, or both, also has a spin and a resulting nuclear magnetic
moment.
– The allowed nuclear spin states are determined by the spin quantum
number, I, of the nucleus given by the formula 2I+1
 •z-component of the angular momentum J

For I=1/2 nuclei, m can only be +1/2 or -1/2, giving rise to two distinct energy
levels. For spins with I=1 nuclei three different values for Jz are allowed:
 •The energy difference E,

• Zeeman effect: splitting of energy levels in

magnetic field
• The energy difference E, which corresponds to the
two states with m=±1/2, is then (the quantum-
mechanical selection rule states, that only
 •POPULATION AND SIGNAL STRENGTH
The strength of the NMR signal depends on the
Population Difference of the two spin states

For a net positive signal

there must be an excess
of spins in the lower state. induced
emission
resonance

excess
population

Saturation = equal populations = no signal

 •Boltzmann Distribution of Spin States

• In a given sample of a specific nucleus, the nuclei

will be distributed throughout the various spin states
available. Because the energy separation between
these states is comparatively small, energy from
thermal collisions is sufficient to place many nuclei
into higher energy spin states. The numbers of
nuclei in each spin state are described by the
Boltzman distribution
 •Boltzmann distribution

• where the N values are the numbers of nuclei in the

respective spin states, is the magnetogyric ratio, h
is Planck's constant, H(B) is the external magnetic
field strength, k is the Boltzmann constant, and T is
the temperature.
• In NMR, the energy separation of the spin states is
comparatively very small and while NMR is very
informative it is considered to be an insensitive
technique .
Example:

• For example, given a sample of 1H nuclei in an

external magnetic field of 1.41 Tesla
• ratio of populations = e((-2.67519x10e8 rad.s-1.T-1 * 1.41T *
6.626176x10-34 J.s) / (1.380662x10e-23 J.K-1 *K 293)) = 0.9999382

• At room temperature, the ratio of the upper to lower

energy populations is 0.9999382. In other words, the
upper and lower energy spin states are almost
equally populated with only a very small excess in
the lower energy state.
•Relaxation processes
• In actual case saturation stage is never
reached because higher energy nuclei are
constantly returning to the lower energy
state by two radiationless processes called
• Spin-spin relaxation
• Spin-lattice relaxation
•SPIN-LATTICE
Relaxation
T1 relaxation is sometimes called spin-lattice
relaxation.
In this type of relaxation the energy lost as the
nucleus returns to the lower
energy state is transferred to the molecule in the
form of heat. This means that
the total number of nuclei in the excited state
decreases.
•SPIN-SPIN Relaxation
T2 relaxation is commonly referred as spin-spin
relaxation.
In this type of relaxation the energy released when a nucleus
makes the transition from high to low energy state is
absorbed by another nucleus. This allows the other nucleus
to move from low energy to high. In this case the total
number of nuclei in the excited state doesn’t change.
Short relaxation times result in broad signals. This is a result
of the Heisenberg uncertainty principle. The shorter the
time frame for observation the more uncertainty exists in
the
. frequency. Longer relaxation times then produce
narrower signals.
 Molecular Symmetry

COURSE NAME:Molecular Spectroscopy

COURSE CODE: 4024577-2
Introduction

The symmetry properties of molecules are

very important to know how to predict
vibrational spectra, hybridization, optical
activity, etc.
 Point Groups
Molecules are classified and grouped
based on their symmetry. Molecules with
similar symmetry are but into the same
point group. A point group contains all
objects that have the same symmetry
elements.
 Symmetry Elements
Symmetry elements are mirror planes,
axis of rotation, centers of inversion, etc.

A molecule has a given symmetry

element if the operation leaves the molecule
appearing as if nothing has changed (even
though atoms and bonds may have been
moved.)
 Symmetry Elements

Element Symmetry Operation Symbol

Identity E
n-fold axis Rotation by 2π/n Cn
Mirror plane Reflection σ
Center of in- Inversion i
version
n-fold axis of Rotation by 2π/n Sn
improper rotation followed by reflection
perpendicular to the
axis of rotation
 Identity, E
All molecules have Identity. This
operation leaves the entire molecule
unchanged. A highly asymmetric molecule
such as a tetrahedral carbon with 4 different
groups attached has only identity, and no
other symmetry elements.
n-fold Rotation
Water has a 2-fold axis
of rotation. When
rotated by 180o, the
hydrogen atoms trade
places, but the molecule
will look exactly the
same.
 n-fold Axis of Rotation

Ammonia has a C3 axis. Note that there are two

operations associated with the C3 axis. Rotation by
120o in a clockwise or a counterclockwise direction
provide two different orientations of the molecule.
Mirror Planes
The reflection of the
water molecule in either of
its two mirror planes results
in a molecule that looks
unchanged.
Mirror Planes
The subscript “v” in σv,
indicates a vertical plane of
symmetry. This indicates
that the mirror plane
includes the principal axis
of rotation (C2).
 Mirror Planes
The benzene ring has a
C6 axis as its principal axis
of rotation.
C6. The molecular plane is
perpendicular to the C6 axis,
and is designated as a
horizontal plane, σh.
 Mirror Planes
The vertical planes, σv,
go through the carbon
atoms, and include the C6
axis.
C6.
The planes that bisect
the bonds are called
dihedral planes, σd.
 Inversion
The inversion operation projects each atom
through the center of inversion, and across to
the other side of the molecule.
 Improper Rotation
An improper rotation is rotation, followed
by reflection in the plane perpendicular to the
axis of rotation.
 Improper Rotation
The staggered
conformation of
ethane has an S6 axis
that goes through
both carbon atoms.
 Improper Rotation

Note that an S1
axis doesn’t exist; it
is same as a mirror
plane.
 Improper Rotation

Likewise, an S2
axis is a center of
inversion.
 Point Groups
Molecules with the same symmetry
elements are placed into point groups.
Point Groups
 Point Groups
In general, you will not need to assign a
molecule to its point group. Recognition of
the features of some common point groups
is useful.
Point Groups
Water and
ammonia both
belong to the Cnv
class of molecules.
These have vertical
planes of reflection,
but no horizontal
planes.
Point Groups
Y
The Dnh groups
X
have a horizontal X
plane in addition to
vertical planes. X
Many inorganic X
complexes belong to
Y
these symmetry
groups.
 Point Groups
Highly symmetrical molecules, such as
identically substituted tetrahedrons or
octahedrons belong to their own point
groups (Td or Oh respectively).
 Point Groups
In assigning a point group, we typically
ignore the fine detail, such as conformation
isomers, of the ligands.
In working problems using group
theory, the point group of the molecule will
usually be provided to you.
 Character Tables
The symmetry properties of each point
group are summarized on a character table.
The character table lists all of the symmetry
elements of the group, along with a
complete set of irreducible representations.
 Character Tables for Point Groups
Each point group has a complete set of possible symmetry operations that are
conveniently listed as a matrix known as a Character Table. As an example, we
will look at the character table for the C2v point group.

Point Group Label Symmetry Operations – The Order is the total number of operations
In C2v the order is 4:
1 E, 1 C2, 1 v and 1 ’v
C2V E C2 v (xz) ’v (yz)
A1 1 1 1 1
A2 1 1 -1 -1 Character
B1 1 -1 1 -1
B2 1 -1 -1 1 Representation of B2

Symmetry Representation Labels

Representations are subsets of the complete point group – they indicate the effect
of the symmetry operations on different kinds of mathematical functions.
Representations are orthogonal to one another. The Character is an integer that
indicates the effect of an operation in a given representation.
 Character Table (C2v)

The functions to the right are called basis

functions. They represent mathematical functions
such as orbitals, rotations, etc.
The px orbital
If a px orbital on the
central atom of a
molecule with C2v
symmetry is rotated
about the C2 axis, the
orbital is reversed, so
the character will be -1.
 The px orbital
If a px orbital on the central atom of a molecule
with C2v symmetry is rotated about the C2 axis, the
orbital is reversed, so the character will be -1.
The px orbital
If a px orbital on
the central atom of a
molecule with C2v
symmetry is
reflected in the yz
plane, the orbital is
also reversed, and
the character will be
-1.
 The px orbital
If a px orbital on the central atom of a molecule
with C2v symmetry is reflected in the yz plane, the
orbital is also reversed, and the character will be -1.
 The px orbital
If a px orbital on the central atom of a molecule
with C2v symmetry is reflected in the xz plane, the
orbital is unchanged, so the character is +1.
Character Table Representations
1. Characters of +1 indicate that the basis
function is unchanged by the symmetry
operation.
2. Characters of -1 indicate that the basis
function is reversed by the symmetry
operation.
3. Characters of 0 indicate that the basis function
undergoes a more complicated change.
 Character Table Representations
1. An A representation indicates that the
functions are symmetric with respect to
rotation about the principal axis of rotation.
2. B representations are asymmetric with respect
to rotation about the principal axis.
3. E representations are doubly degenerate.
4. T representations are triply degenerate.
5. Subscrips u and g indicate asymmetric
(ungerade) or symmetric (gerade) with respect
to a center of inversion.
 Applications of Group Theory
1. Predicting polarity of molecules. A
molecule cannot have a permanent dipole
moment if it
a) has a center of inversion
b) belongs to any of the D point groups
c) belongs to the cubic groups T or O
 Applications of Group Theory
2. Predicting chirality of molecules. Chiral
molecules lack an improper axis of rotation
(Sn), a center of symmetry (i) or a mirror
plane (σ).
 Applications of Group Theory
3. Predicting the orbitals used in σ bonds.
Group theory can be used to predict which
orbitals on a central atom can be mixed to
create hybrid orbitals.
 Applications of Group Theory
4. Predicting the orbitals used in molecular
orbitals. Molecular orbitals result from the
combining or overlap of atomic orbitals,
and they encompass the entire molecule.
 Applications of Group Theory
5. Determining the symmetry properties of all
molecular motion (rotations, translations
and vibrations). Group theory can be used
to predict which molecular vibrations will
be seen in the infrared or Raman spectra.
 Molecular Vibrations
Molecular motion includes translations,
rotations and vibrations. The total number
of degrees of freedom (types of molecular
motion) is equal to 3N, where N is the
number of atoms in the molecule.
 Molecular Vibrations
Of the 3N types of motion, three
represent molecular translations in the x, y
or z directions. Linear molecules have two
rotational degrees of freedom, and non-
linear molecules have three rotational
degrees of freedom.
 Molecular Vibrations
For linear molecules, the number of
molecular vibrations = 3N-3-2 = 3N-5.

For non-linear molecules, the number of

molecular vibrations = 3N-3-3= 3N-6.
 Molecular Vibrations
To obtain Гred for all molecular motion, we
must consider the symmetry properties of the
three cartesian coordinates on all atoms of the
molecule.
 Molecular Vibrations
z y
x

The molecule lies in the xz plane. The x

axis is drawn in blue, and the y axis is drawn
in black. The red arrows indicate the z axis.
 Molecular Vibrations
y
x

The molecule lies in the xz plane. The x

axis is drawn in blue, and the y axis is drawn
in black. The red arrows indicate the z axis.
 Molecular Vibrations
z y
x

If a symmetry operation changes the

position of an atom, all three cartesian
coordinates contribute a value of 0.
Vibrational Modes in CO2

For linear molecules: 3N - 5 IR fundamentals

Vibrational Modes in SO2

For non-linear molecules: 3N - 6 IR fundamentals