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1- Text Book,
Fundamental of Molecular
Spectroscopy, C. N. Banwell, 4 th
2- Internet website

may be defined
as the study of
the interaction
c Waves and

We shall be concerned

What spectroscopy can tell us of the

structure of matter

Nature of electromagnetic radiation

How the interaction of

electromagnetic and matter is

Frequencies: are always expressed

in Hz (after Hertz) with the unit
1/second ("cycles" is derived from
Hz and only used for cyclic
movements. In one second how
many cycle is travelled.

Wavelengths are expressed in different

units. (The distance travelled during a
complete cycle) (ngstrom, 10-10 m) is
common for short wavelengths: g-rays, Xrays, up short wavelength UV ("vacuum
UV") nm (10-9 m) is common for UV-Vis
(350 nm - 800 nm) cm are used for
microwave spectroscopy.

Wave numbers (1/)

E = h and = c/
E = hc/~<

Energies are expressed in different

units. eV (electron volts) for
atomic spectroscopy, photoelectron
spectroscopy, mass spectroscopy, 1
eV is the energy that an electron
acquires after passing through a
voltage difference of one volt.

The Quantization of Energy

The energy of an oscillator (absorbed or emitted) is not continuous
and that any change in its energy can occur only by means of a jump
between two distinct energy states i.e., it is quantized.
; A molecule in space can have many sorts of energy
Rotational energy:- by virtue of bodily rotation about its center of-1
Vibrational energy:- due to the periodic displacement of its atoms-2
.from their equilibrium positions
Electronic Energy:- due to transfer of electrons associated with its-3
.atoms or bonds between available energy levels
Transitional Energy:- due to free movement of the whole- 4
.molecule in the space
All the above energies of the molecule are quantized except the
.Transitional Energy

E = E2 - E1 = h
is the frequency
of the light photon

i- Symmetric stretching vibration;

The dipole moment remains
**infra-red inactiv **

Antisymmetrical stretch,
there is a periodic
in the dipole moment,

infra-red active**


1- What is the role of Spectroscopy?

2- Define and\or characterize:Molecular energies, light, Quantized energy, IRactive molecule.
3- Arrange the following spectral regions
according to increase in energy (start with
smallest), Radio wave, x-rays, visible rays, Which
region can only produce n.m.r spectra?
4- Show by diagrams only how a vibrating
molecule can interact with light


Problems 1.1 and 1.2 page 39 (Banwell)

Representation of Spectra
Generally, the spectral band is characterized by
. position, width, and intensity

ition of the spectral bands, or the frequencies at which the molecule absorb
s on its structural features ( Functional group) as well as on its environment

The two most important features of**

:- spectral lines are
their height (~ intensity) and their
.width (n)

I- Width
There are two factors cause the width broadening
1- Factors related to an instrumental defect
a) Signal to noise ratio S/N (4/1)

In order to detect the real sample signal from the instrument noise, .
the intensity of this signal should be Four times that of noise.

b) Shape and Resolution

A crucial question that arises with any spectroscopic
technique is the question of how well we will be able
to resolve two different spectral lines

2- Natural Broadening ( Deformation of molecular orbitals)

a) Collision Broadening
1- The collision of molecules causes the excited state to revert to the ground state

2- Collisions thus shorten the lifetimes of excited states and lead to the broadening of the associated spectral lines.

b) Doppler Broadening

* The frequency that an object emits is modified by its speed relative to the observer (detector).

** It

is possible to eliminate Doppler broadening by investigating a molecular beam of the

atoms / molecules and placing the detector at a 90 deg angle to the direction of the beam.

c) Heisenberg Uncertainty Principle ( E t > h / 4 10


J s)

Heisenberg Uncertainty Principle

II- Intensity
:- Transition Probability- 1
The precise calculation of transition probabilities is involved and requires
quantum mechanics. However, it is often possible to predict if a transition is
symmetry allowed or forbidden. We will discuss the respective Selection
.Rules for each spectroscopic technique individually

:- Population of States- 2
For thermal equilibrium, the probability of a state in thermal equilibrium is given
:by the Boltzmann Distribution
Nupper / Nlower = exp(-E/kT)

The Concentration or path length of the sample -3

log [ I/Io] = c e l - ( Lambert-Beer's Law(


(Light Amplification by Stimulated

Emission of Radiation)

Properties of Laser Light

Laser light differs in many aspects from ordinary light (that is: the light
generated by light bulbs or fluorescent tubes). Laser light is
Monochromatic The range of frequencies emitted by a laser is very- 1
. narrow,typically Dn / n = 10-5 to 10-8
Low Divergence Laser beams can not only be focused to a smaller- 2
point than any other light source (ca. 1 l), but the also show very small
divergence. Under optimum conditions, the divergence can reach the
theoretical limit of f = l / d
Coherent The maxima and minima of all emitted wavelets occur at - 3
. the same position
Highly Intense Pulsed lasers can generate light pulses of extremely- 4
high intensity. For example, commercially available Nd:YAG lasers (l =
1064 nm) are capable of 10 ns pulses with an energy of 108 W. This
corresponds to an energy of 1020W / m2 at the focal point - 1017 (!)
. times more intense than the sunlight at the earth's surface
Polarized The E-planes of the individual light waves are all parallel to - 5
. each other
Precisely Timed The ability to create incredibly short laser pulses - 6
(currently: 4 femtoseconds = 4 fs = 4 x 10-15 s) allows the spectroscopic
resolution of extremely fast processes. A 4 fs pulse in the visible
. corresponds to only 2 cycles of the corresponding sin wave