Group 1 Assignment

Course Title:

Quantum Chemistry and Molecular Spectroscopy

Topic:

Interaction of Electromagnetic radiation and Matter & Symmetry

Properties of Molecules

Submitted to: Dr. Sehrish Mehdi

Submitted by:

Zarish Maqbool (BCHE-20-27)

Mariyam Roshan (BCHE-20-59)

Umayyah Khan (BCHE-20-76)

Sanna Jabbar (BCHE-20-92)

Arfa Zia (BCHE-20-46)

Robina Iqbal (BCHE-20-50)

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1. Interaction of Electromagnetic radiation and Matter
Whenever Electromagnetic radiation interacts with matter, changes can occur in both
electromagnetic radiation as well as matter. The interaction of electromagnetic radiation with
matter is also called Spectroscopy.

1.1 When Matter interacts with Electromagnetic radiation:

Figure 1.1 Interaction of matter with electromagnetic radiation

1.2 When Electromagnetic radiation interacts with Matter:

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Figure 1.2 Interaction of Electromagnetic radiation with matter [2]

1.3 Electromagnetic Spectrum:

Electromagnetic spectrum is the continuous spectrum of all forms of electromagnetic radiation

according to frequency or wavelength.

Figure 1.3 Electromagnetic spectrum showing different electromagnetic radiations.

1.4 Absorption based Methods:

The energy carried out by a photon is absorbed by analyte, promoting the analyte from lower
energy state to a higher energy state. Absorption only occurs when the energy of photon becomes
equal to the energy difference between two energy levels. .

 Microwave absorption spectroscopy:

Microwave absorption spectroscopy uses microwave radiation to analyze transitions between

molecular rotational energy levels, thus providing information on accurate molecular geometries.

 Infrared absorption spectroscopy:

Infrared radiation promotes transitions between vibrational energy levels, leading to spectra that
allows for the identification of functional groups which represent a very characteristic and
sensitive fingerprint of a specific molecule.

 Visible and UV absorption spectroscopy:

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Absorption of atoms and molecules with visible and near-UV light can lead to transition of
electronic energy levels providing information on their electronic structure. Its most extended
use is in quantitative analysis.

 X Ray absorption spectroscopy:

X-ray absorption spectroscopy (XAS) is another example, which provides information on the
energies of core electrons (it can be used to identify atoms) as X rays knock out inner shell
electrons on interacting with matter.

1.5 Emission based Methods:

A photon is generated while the energy in the medium decreases by hν. For this to happen, the
atom, molecule, or material needs to be in an excited state, emitting radiation in the decay to the
ground state (or a less energetic state). The initial excitation can be achieved thermally, by
collision with a beam of Particles, and so on.

 Atomic Emission Spectroscopy:

In atomic emission spectroscopy, energy is applied to a molecule in form of light or heat. This
energy then excites the electrons in atoms to a higher energy level. The excited state is, however,
less stable than the ground state of an atom, this results in decay of the excited state. It is used for
both Qualitative and Quantitative analysis.

 Fluorescence Spectroscopy

In Fluorescence spectroscopy, the excitation of the material is produced by incoming

electromagnetic radiation, and the radiation emitted has a very small delay and a lower frequency
than the incoming light due to loss of energy in the form of heat or vibration.

e.g. X Ray Fluorescence Spectroscopy is used for elemental analysis in materials

 Phosphorescence Spectroscopy:

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 Figure 1.4 Diagram showing different types of Spectroscopy

Phosphorescence Spectroscopy is same as Fluorescence but the process of emitting radiation is

relatively slower. It’s also called delayed emission.

1.6 Diffraction and Scattering Methods:

1.6.1 Scattering:

Scattering is the process in which energy is absorbed from a beam of electromagnetic radiation and
re-emitted with a change in direction, phase, or wavelength. Scattering of Electromagnetic radiation
can be elastic and Inelastic.

 Elastic Scattering:

If the wavelength of scattered radiation is same as the wavelength of incident beam, then the
radiation is scattered elastically. Elastic Scattering is furthur subdivided into Rayleigh Scattering
and Mie Scattering.

 Rayleigh Scattering: In Rayleigh Scattering, Wavelength of incoming radiation is larger than the
Particle Size of matter.
 Mie Scattering: In Mie Scattering, wavelength of incoming radiation is similar to the Particle Size
of matter.
 Inelastic Scattering

If the frequency of scattered radiation is different than the frequency of incoming beam, then the
radiation is said to be inelastic. It is also called Ramen Scattering. Ramen Scattering is furthur
subdivided into stokes and antistokes scattering.

 Stokes Scattering: When the Frequency of incident beam is greater than the frequency of scattered
beam, then this type of scattering is called Stokes Scattering.
 Antistokes scattering: When the Frequency of incident beam is smaller than the frequency of scattered
beam, then this scattering is called antistokes Scattering.

1.6.2 Diffraction

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 Diffraction is the process of light bending around an obstacle or spreading out after it moves
through a small space.

 X-ray diffraction is a technique used to study the arrangement of atoms in a crystal

lattice. When X-rays pass through a crystal, they diffract, creating a unique pattern that can
be analyzed to determine the crystal’s structure. This method is an essential tool in the
structural elucidation of crystals.
 Electron diffraction (usually carried out in a transmission electron microscope),
similar to X-ray diffraction but uses electrons instead of X-rays. When electrons are
accelerated and directed at a sample, they undergo diffraction, producing a pattern that can
be used to analyze the sample’s structure, particularly at the atomic level, providing
information about both long-range and short-range order in solids.[1]

2. The Symmetry of Molecules

2.1 Symmetry Elements:

Figure 1.5 Symmetry Elements

A symmetry operation is an action that leaves an object looking the same after it
has been carried out. For example, if we take a Molecule of water and rotate it by
180° about an axis passing through the central O atom (between the two H atoms)
it will look the Same as before. Each symmetry operation has a corresponding

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symmetry element, which is the axis, plane (2-dimensional), line (1-Dimensional)
or point (0-dimensional) with respect to which the symmetry operation is carried
out:

These above 3 are the symmetry element around which symmetry operations are

performed like rotation, reflection, etc .

2.2 Symmetry Operations:

The symmetry of a molecule or ion can be described in terms of the complete

collection of symmetry operations it possesses. There are five types of operations:

 Identity
 Rotation
 Reflection
 Inversion
 Improper Rotation

A symmetry operation is a permutation of atoms such that the molecule is

transformed into a state indistinguishable from the Starting state.

 Identity Symmetry, E

The identity operator, , consists of doing nothing, and the corresponding symmetry
element is the entire molecule. Every Molecule possesses at least this operation.

The identity symmetry Operation is not indicated since all molecule exhibit this
symmetry.

 n-fold Axis of Rotation, Cn

The rotation operation (sometimes called proper rotation), , rotates an object about
an axis by 360 degree leaves the molecule unchanged. Molecules can have more

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than one Cn axis, in which case the one with the highest value of n is called the
principal axis. In some high symmetry systems, there may be more than one
principal axis.

Linear molecules have a very high rotational symmetry. Examples include

diatomics such as CO.

 Reflection, (σ )

Reflection defines the bilateral symmetry about a plane (mirror plane / reflection
plane).

Reflection in the plane also leaves the molecule looking the same forming identical
mirror image. In a molecule that also has an axis of symmetry, a mirror plane that
includes the axis is called a vertical Mirror , while one perpendicular to the axis is
called a horizontal mirror plane .

A Vertical Mirror plane that bisects the angle between two axes is called a dihedral
mirror plane, .

The water molecule contains Two different reflection planes. Benzene contains a
total of seven reflection planes, one horizontal plane and six vertical planes.

 Inversion, î

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. If inversion symmetry exists, a
line drawn from any atom through the center will connect with an equivalent atom
at an equivalent distance from the center.

E.g. Methane exhibit inversion symmetry.

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 The Inversion center is always located at the central point of the molecule and
there can only be one inversion center in any system.

Performing inversion twice in succession brings every point back to its original
position.

 n-fold Axis of Improper Rotation, Sn

Improper rotations, , are also called rotation-reflections. The rotation-reflection

operation consists of rotating a molecule about an Axis, followed by reflecting in a
plane perpendicular to the same axis. Improper rotation symmetry is indicated with
both an axis and a plane. [3]

Table 1.1 Symmetry operators with brief description

References

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1. https://application.wiley-vch.de/books/sample/3527333363_c01.pdf
2. http://hyperphysics.phy-astr.gsu.edu/hbase/mod3.html
3. https://chem.libretexts.org/Courses/University_of_California_Davis/Chem_110B
%3A_Physical_Chemistry_II/Text/12%3A_Group_Theory_-_Exploiting_Symmetry/
12.2%3A_The_Symmetry_of_Molecules
… … … ….. …… … … … … … … … … .

Short Questions

1. How many reflection planes does benzene consist of?

Answer: Benzene consists of total seven reflection planes: one of them is horizontal while six are
vertical planes

2. What is symmetry operation?

Answer: A symmetry operation is an action that leaves an object looking the same after it has been
carried out. For example, if we take a molecule of water and rotate it by 180° about an axis passing
through the central O atom (between the two H atoms) it will look the Same as before.

3. Each symmetry operation has a corresponding symmetry element. What are they?

Answer: Each symmetry operation has a corresponding symmetry element, which is the axis, plane
(2-dimensional), line (1-Dimensional) or point (0-dimensional) with respect to which the symmetry
operation is carried out.

4. What is the basic difference between x ray diffraction and x ray diffraction?

Answer:

 X-ray diffraction is a technique used to study the arrangement of atoms in a crystal lattice.
When X-rays pass through a crystal, they diffract, creating a unique pattern that can be
analyzed to determine the crystal’s structure.

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  Electron diffraction (usually carried out in a transmission electron microscope), similar to
X-ray diffraction but uses electrons instead of X-rays. When electrons are accelerated and
directed at a sample, they undergo diffraction, producing a pattern that can be used to
analyze the sample’s structure, particularly at the atomic level, providing information about
both long-range and short-range order in solids.
5. What are the types of Electromagnetic radiation?

Answer: Electromagnetic radiation is classified into different types according to the frequency and
wavelength. These types include (in order of increasing frequency): radio waves, microwaves,
infrared radiation, visible light, ultraviolet radiation, X-rays and gamma rays.

Multiple Choice Questions:

1. n fold axis of rotation represent which one:

a. no change

b. rotation by 360°✅

c. rotation and reflection

d. inversion
2. Methane exhibits which of the following symmetry?
a. Identity symmetry.
b. Centre of symmetry.

c. Inversion symmetry✅

d. Plane of symmetry
3. X ray absorption spectroscopy provides information about:

a. Energies of core electrons ✅

b. Electronic structure
c. Identification of functional group
d. transition

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4. Microwave absorption spectroscopy gives information about:

a. Accurate molecular geometries✅

b. Orbital levels
c. Energy levels
d. Transition levels
5. IR leads to:
a. Identification of functional group
b. Represents fingerprints of specific molecules

c. Both a & b✅

d. None of these

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