Electromagnetic Radiation (EMR)

How the energy travel trough the space?

What is EMR?

 EMR is a form of energy that is transmitted through space at an enormous velocity.

 It can travel in space with the same speed at that of light.
 As the name implies an EMR is an alternating electrical and associated magnetic force
field in space (It contains electrical and magnetic components).
 The two components oscillate in planes perpendicular to each other and perpendicular
to the direction of propagation of the radiation.
 EMR consist of a stream of discrete packets (particles) of pure energy, which is called
photons or quanta.
 The energy of photon is proportional to the frequency
E = hυ
where E= Energy of photons, h= plank’s constant (6.624 x 10 -27 erg. Sec)
and υ=frequency of radiation in cycles/second

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 Wavelength: The distance between two successive crests or troughs of a wave
and denoted by the Greek letter λ (lambda).
Unit: m, cm, mm, μm, nm, and A0
Frequency: The number of waves (cycles or oscillation) per second that pass a
given point in space. Symbolized by the lowercase Greek letter nu, ν.

Unit: sec-1, cycles/second, hertz (Hz), kilohertz (KHz), megahertz (MHz),

gigahertz (GHz)
The speed (or velocity) of a wave is the distance through which a particular wave
travels in one second.
c = νλ
or Speed = Frequency × Wavelength, C= velocity of light or wave = 3.08 x 108 m/s

Wave Number: This is reciprocal of the wavelength and is given the

symbol ν (nu bar). That is,

The wave number is the number of wavelengths per unit of length

covered. Its units are cm–1 or m–1.

A wave of high frequency has a shorter wavelength, while a

wave of low frequency has a longer wavelength.
 Quantization of Energy
 Classical Mechanics: Any real
value of energy is allowed.
Energy can be continuously
varied.
 Quantum Mechanics: Not all
values of energy are allowed.
Energy is discrete (quantized)

An electron can radiate or absorb energy as radiation only in a pulse of energy called quanta or photon. This is known as the quantization of energy
 The Electromagnetic Spectrum
Electromagnetic radiations/spectrum include a range of wavelengths and this array of wavelengths.

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Legend:
γ = Gamma rays

HX = Hard X-rays
SX = Soft X-Rays

EUV = Extreme-ultraviolet
NUV = Near-ultraviolet

Visible light (colored bands)

NIR = Near-infrared
MIR = Mid-infrared
FIR = Far-infrared

EHF = Extremely high frequency (microwaves)

SHF = Super-high frequency (microwaves)

UHF = Ultrahigh frequency (radio waves)

VHF = Very high frequency (radio)
HF = High frequency (radio)
MF = Medium frequency (radio)
LF = Low frequency (radio)
VLF = Very low frequency (radio)
VF = Voice frequency
ULF = Ultra-low frequency (radio)
SLF = Super-low frequency (radio)
ELF = Extremely low frequency(radio)
 Basics of Molecular spectroscopy
Spectroscopy is the study of the interaction of light and matter. Many types of spectroscopy rely on the ability of atoms and molecules
to absorb or emit electromagnetic (EM) radiation. The absorption or emission of different forms of EM radiation is related to different
types of transitions.

A spectrum is a graph that shows the response of materials

(atom, molecule, or ion) to the intensity of radiation at
different wavelengths
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UV radiation and Electronic Excitations
1. The difference in energy between molecular bonding, non-bonding, and anti-bonding orbitals ranges from 125-650 kJ/mol.
2. This energy corresponds to EM radiation in the ultraviolet (UV) region, 100-350 nm, and visible (VIS) regions 350-700 nm of the
spectrum.
Vibrational Excitation
 Using IR we observed vibrational transitions with energies of 8-40 kJ/mol at wavelengths of 2500-15,000 nm.
Rotational Excitation
 Rotational transition with energies of 0.12-0.0012 kJ/mol at wavelengths of 9.96 x 105-9.96 x 107 nm.

Nuclear Spin rotation

 Nuclear spin changes with the energies of the radio frequency region (4-900 MHz) which is in the region of 1.6 x 10-6-3.6 x 10-4
kJ/mol.

g-rays X-rays UV IR Microwave Radio

Visible
 What is signal to noise (S/N) ratio?
Signal-to-noise ratio (SNR or S/N) is a measure used in science and engineering that compares the level of a desired signal
to the level of background noise. SNR is defined as the ratio of signal power to noise power, often expressed in decibels.
How to increase S/N ratio?
1. Signal averaging
2. Using mathematical filters
(digital smoothing filter, moving average filter and
Savitzky-Golay filter).
3. Fourier transform (FT) filtering

What is full-width half-maxima (FWHM)?

Full Width at Half Maximum (FWHM) corresponds to the width of a spectral peak
at half of its maximum amplitude. This can be visualized as the distance between
two points on the y-axis where the curve's intensity is half of its peak value. For
Gaussian line shapes, the FWHM is about 2.4 standard deviations.
Resolution: In spectroscopy, resolution or resolving power is the ability to separate two distinct peaks that are close
together. The resolving power of an optical instrument is its ability to separate the images of two objects, which are close
together.
 Electronic spectroscopy
Ultraviolet-visible (UV-vis) spectroscopy is used to obtain the
absorbance spectra of a compound in solution or as a solid.
What is actually being observed spectroscopically is the
absorbance of light energy or electromagnetic radiation,
which excites electrons from the ground state to the first
singlet excited state of the compound or material. The UV-vis
region of energy for the electromagnetic spectrum covers 1.5
- 6.2 eV which relates to a wavelength range of 800 - 200 nm.

Energy required of photon

to give this transition
DE = E1 - Eo = hn

Color Change Due to Fluorescence

at Higher Wavelength
Basic Concepts in Fluorescence
 The Beer-Lambert law states that the absorbance of a solution is directly proportional to the concentration of the
absorbing species in the solution and the path length. Thus, for a fixed path length, UV/Vis spectroscopy can be used to
determine the concentration of the absorber in a solution. It is necessary to know how quickly the absorbance changes
with concentration.

A = εbc Long pathlength 1 cm pathlength cuvet

where, A = Absorbance (no unit)

ε – molar absorptivity (L/mol-cm)
b – pathlength (cm)
Opaque

and c – molar concentration (mol/L)

Face

Transparent

Absorbance is sometimes called

Face

optical density (OD)

1 cm 1 cm
Short pathlength (b)
Increasing [Fe2+]

Absorbance is directly proportional to concentration of Fe +2

 The process of light being absorbed by a solution

with sample A – absorbance

I < Io A = - log T = -log I/ Io
A   log T   log I / I 0   log I 0 / I     b  c
blank where Io = I

light
source detector

Io I
I – intensity where Io is initial intensity As concentration
b increased, less
T – transmission or %T = 100 x T
light was
(absorption: Abs = 1 – T or %Abs = 100 - %T) Cell with
T = I/ Io transmitted (more
Pathlength, b,
light absorbed).
containing solution
 Applications of Ultraviolet/Visible
Molecular Absorption Spectrophotometry

 Molecular spectroscopy based upon UV-Vis radiation is used

for identification and estimation of inorganic, organic and
biomedical species.
 Molecular UV-Vis absorption spectrophotometry is employed
primarily for quantitative analysis.
 UV/Vis spectrophotometry is probably more widely used in chemical
and clinical laboratories throughout the world than any other single
method.
What Happens When a Molecule Absorbs Light?

1.) Molecule Promoted to a More Energetic Excited State

 Two Possible Transitions in Excited State
- Single state – electron spins opposed
- Triplet state – electron spins are parallel
 In general, triplet state has lower energy than singlet state

 Singlet to Triplet transition has a very low probability

 Singlet to Singlet Transition are more probable