Unit 1

Introduction of spectroscopic methods

Introduction: Spectroscopy is the branch of science dealing with the study of interaction
ofelectromagnetic radiation with matter like atoms and molecules. The interaction of EMR with
matter gives rise to two types of spectra namely atomic spectra and molecular spectra.

Atomic spectrum arises from the transition of electrons from one energy level to another
due to changes of energy in the atom.

Molecular spectrum involves transition of electrons between rotational and vibrationalenergy

levels in addition to electronic transition. Therefore molecular spectrum is much more complicated
than the atomic spectrum.

Molecular Spectroscopy provides a clear image of how diatomic and polyatomic molecules
interact by looking at the Frequency, Wavelength, Wave number, Energy, and molecular process also
provides most useful information regarding the shape and size of molecules, the bond angles, bond
lengths, strength of bonds and bond dissociation energies.

Hence molecular spectroscopy is of great use in determining the structure and constitution
of compounds.

Electromagnetic Radiations (EMR)

EM radiation is created when a subatomic particle, such as an electron, is accelerated by an electric

field. The movement produces oscillating electric and magnetic fields, which travel at right angles to
each other in a bundle of light energy called a photon. Photons travel as harmonic waves at the fastest
speed possible in the universe: 186,282 miles per second (299,792,458 meters per second) in a
vacuum, also known as the speed of light.

The EM waves are characterized by frequency, wavelength, wave number and energy.

Electromagnetic (EM) radiation is a form of energy that is all around us and takes many forms, such
as radio waves, microwaves, X-rays and gamma rays.

Visible light is only a small portion of the EM spectrum, which contains a broad range of
electromagnetic wavelengths.
Electromagnetic waves are formed when an electric field (shown in red arrows) couples with a
magnetic field (shown in blue arrows). Magnetic and electric fields of an electromagnetic wave are
perpendicular to each other and to the direction of the wave.

The four main electromagnetic interactions:

The force of attraction or repulsion between electric charges is inversely proportional to the square
of the distance between them.

Magnetic poles come in pairs that attract and repel each other, similar to that of electrical charges.

An electric current in a wire produces a magnetic field, the direction of which depends on the
direction of the current.

A moving electric field produces a magnetic field, and vice versa.

Characterization of EMR

Wavelength (λ) : It is the distance between two consecutive peaks of a wave (crests). Unit = m.

Frequency (√): It is the number of waves that are formed in a given length of time. Unit =
number of wave cycles per second or hertz (Hz).

A short wavelength means that the frequency will be higher and a longer wavelength has a lower
frequency.

Wavenumber (ῡ ): It is the number of waves per unit distance. Unit = cm-1 ῡ = 1/

λ

Energy of EMR (E):Electromagnetic radiations consists of particles having small packets of

energies called quanta or photons. Photons possess the characteristic of wave and travel with the
speed of light. The amount of energy corresponding to one photon is expressed by Planck’s equation
as

E
=
h
ν
where h = Planck’s constant (6.62x10-34Js)

ν - frequency in Hz

λ - wavelength in cm/m.

Energy (E) = hc/λ

E = h√

E = hcῡ

Interaction of EMR with matter

EMR interacts with matter only when the matter has some electric and magnetic effect and are
influenced by the electric and magnetic components of the EM radiation.

The net change in the electric/magnetic dipole moment in the molecule or nuclear spin, interact
with the magnetic/electrical component of the EMR by either absorption or emission of the EMR.

Total energy of molecules = Translational + rotational + vibrational + electronic

Absorption or emission of EMR causes a change in any of these types of energies.

In molecular spectroscopy, we measure the change in these energy states.

Translational energy – It is due to the overall movement of the molecule. Energy levels are not
quantized . Hence no spectroscopy.

Rotational energy – It is due to spinning of molecules about the axis passing through the centre of
gravity - Rotational Levels are quantized – Rotational spectroscopy (Microwave spectroscopy)
Vibrational energy – It is due to vibrations in molecules – Vibrational Levels are Quantized – IR
Spectroscopy (Vibrational spectroscopy)

Electronic energy – Consists of electronic levels which are quantized – UV/visible spectroscopy
(Electronic spectroscopy)

If E is the total energy of a molecule, it can be expressed as the sum of translational, rotational,
vibrational and electronic contributions. E = Etrans +Erot + Evib + Eelec

Spectra

Molecular spectra result from either the absorption or the emission of electromagnetic radiation as
molecules undergo changes from one quantized energy state to another.

• The electrons in a molecule possess kinetic energy due to their motions and potential energy
arising from their attraction by the positive nuclei and their mutual repulsion. These two
energy factors, along with the potential energy due to the mutual electrostatic repulsion of the
positive nuclei, constitute the electronic energy of a molecule.
• Molecules are not rigid structures, and the motion of the nuclei within the molecular
framework gives rise to vibrational energy levels.
• In the gas phase, where they are widely separated relative to their size, molecules can undergo
free rotation and as a result possess quantized amounts of rotational energy.
• In theory, the translational energy of molecules through space is also quantized, but in
practice the quantum effects are so small that they are not observable, and the motion appears
continuous.
 • The interaction of electromagnetic radiation with these molecular energy
levels constitutes the basis for Electronic, IR and Microwave spectroscopy.

Absorption and Emission Spectra

Absorption of electromagnetic radiation by compounds gives absorption spectrum and spectrum

obtained by the emission of absorbed radiation is called emission spectrum.

Ground level/state is the lowest energy state. Higher energy levels/states are called excited states.

QUANTIZATION OF ENERGY LEVELS

Selection Rule in Spectroscopy

Selection rules describe the allowed transitions between energy states in quantum systems.
Theyare determined by which final states are accessible given an initial state and perturbing
potential.

Atomic and molecular species contain a very large number of states in which energy can
bedistributed, although generally only the states lying lowest in energy will be thermally
populated.

If electromagnetic radiation could effectively stimulate transitions between any one of

thesestates, atomic and molecular spectra would be complex.

Selection rules, limit the possible transitions and render these spectra amenable to

analysis.Some transitions are “allowed” by the selection rules, while others are

“forbidden”.

• The selection rules may differ according to the technique used to observe the transition.
• In quantum mechanics the basis for a spectroscopic selection rule is the value of
the transition moment integral

• where Ψ1 and Ψ2 are the wave functions of the two states, "state 1" and "state 2", involved
in the transition, and µ is the transition moment operator. This integral represents
the propagator (and thus the probability) of the transition between states 1 and 2; if the value
of this integral is zero then the transition is “forbidden".
• In practice, to determine a selection rule the integral itself does not need to be calculated: It
is sufficient to determine the symmetry of the transition moment function. If the transition
moment function is symmetric over all of the totally symmetric representation of the point
group to which the atom or molecule belongs, then the integral's value is (in general)
not zero and the transition is allowed. Otherwise, the transition is “forbidden”.
• The transition moment integral is zero if the transition moment function, is anti-symmetric
or odd.

Width of Spectral lines

Spectral lines are broadened because of two reasons:

1. Energy levels are not sharp.

2. Atoms are moving relative to observer.

Three mechanisms determine the line profile –

1. Quantum mechanical uncertainty in the energy E of levels with finite lifetimes.
Determinesthe natural width of a line (generally very small).
2. Collisional broadening: Collisions reduce the effective lifetime of a state, leading to
broaderlines. High pressure gives more collisions (eg stars).
3. Doppler or thermal broadening, due to the thermal (or large-scale turbulent) motion
ofindividual atoms in the gas relative to the observer.
Chemical analysis:
Chemical analysis is a method of Separation, Identification and Quantification of different
components present in the given sample by using different analytical techniques.
Classification of methods: Chemical analysis is mainly of two types.
1. Qualitative chemical analysis
2. Quantitative chemical analysis
1. Qualitative analysis:
 Identification of analytes is being carried out by using different analytical methods.
 Inorganic Simple salt analysis and Mixture analysis for identification of different anions
and cations present in the given unknown sample.
 Organic Compound analysis for identification of different functional groups present in
the given unknown compound
2. Quantitative analysis, in which the quantification of analytes is being carried out by using
different analytical techniques.
• Gravimetric analysis
• Titrimetric analysis
• Volumetric analysis
• Spectrophotometric analysis, etc
 Quantitative analysis, is further classified into two types-
1. Classical methods of analysis
2. Instrumental methods of analysis
Classical methods: These are conventional type of methods for quantitative determination of
analytes. Ex: Gravimetric methods, Titrimetric methods, etc.
 Classical methods of analysis is also termed as wet chemical analysis, consists of those
analytical techniques that use no mechanical or electronic instruments other than a
balance.
 The classical methods of analysis is usually relies on chemical reactions between the
material being analyzed (the analyte) and a reagent that is added to the analyte.
Instrumental Methods: In contrast to Classical methods, Instrumental methods of analysis
typically depends on the measurement of a physical property of the particular analyte by using an
instrument.
  It involves the use of an instrument, other than a balance, to perform the analysis. In
some cases, the instrument is used to characterize a chemical reaction between the
analyte and an added reagent; in others, it is used to measure a property of the analyte.
 Instrumental Methods: • Conduct metric titrations, • pH metric titrations, •
Potentiometric titrations, • Spectroscopic methods, • Thermal Methods, • Electro
analytical methods, etc.

Types of Instrumental Methods:

1. Examples of Spectroscopic Instrumental Methods That Involve an Exchange of Energy Between
a Photon and the Sample
type of energy transfer region of electromagnetic spectroscopic technique
spectrum
absorption γ-ray Mossbauer spectroscopy

X-ray X-ray absorption spectroscopy

UV/Vis UV/Vis spectroscopy

IR infrared spectroscopy

microwave raman spectroscopy

radio wave electron spin resonance

nuclear magnetic resonance

emission (thermal UV/Vis atomic emission spectroscopy

excitation)
photoluminescence X-ray X-ray fluorescence

UV/Vis fluorescence spectroscopy

phosphorescence spectroscopy

atomic fluorescence spectroscopy

chemiluminescence UV/Vis chemiluminescence spectroscopy

2. Additional Examples of Instrumental Methods of Analysis

type of measurement or phenomenon instrumental method
piezoelectric effect quartz crystal microbalance
mass-to-charge ratio mass spectrometry
 rate of chemical reaction or physical process kinetic methods

flow injection analysis

neutron activation analysis

isotope diution analysis

thermal energy thermal gravimetry

differential thermal analysis

differential scanning calorimetry

gas chromatography

equilibrium partitioning between two phases liquid chromatography

supercritical fluid chromatography

migration in response to applied electrical field electrophoresis