Fundamentals of Spectroscopy

Chemists, physicists, biochemists, and other scientists are deeply interested in knowing the
structure of molecules. The knowledge about molecular structure is derived indirectly from
the technique known as spectroscopy which deals with the transitions that a molecule
undergoes between its energy levels upon absorption of suitable radiations determined by
quantum mechanical selection rules.
How does a spectrum arise?
Consider two molecular energy levels En and Em,. If a photon of frequency v falls on a
molecule in the ground state and its energy hν is exactly equal to the energy difference ∆E=
(Em - En) between the two molecular energy levels, then the molecule undergoes a transition
from the lower energy level to the higher energy level with the absorption of a photon of
energy hν. The spectrum thus obtained is called the absorption spectrum. If the molecule falls
from the excited state to the ground state with the emission of a photon of energy hν, the
spectrum obtained is called the emission spectrum.

The compounds with covalent bonds, whether organic or inorganic, absorb various
electromagnetic radiation frequencies in the electromagnetic spectrum's (IR). This region lies
between visible light and microwaves. For chemical purposes, we are interested in the
vibrational portion of the infrared region. It includes radiation with wavelengths (l) between
2.5 µm and 15 µm. Here the wavelength, λ is inversely proportional to the frequency, γ and
is governed by the relationship γ = c/ λ , where c = speed of light. Also observe that the
energy is directly proportional to the frequency: E = h λ , where h = Planck’s constant.
 Most chemists refer to the radiation in the vibrational infrared region of the electromagnetic
spectrum in terms of a unit called a wavenumber Wavenumbers are expressed as reciprocal
centimeters (cm−1)

Width and Intensity of Spectral Lines

When we analyze the spectrum of a molecule, we see a sharp spectral line having no width
and a spectral line having a width ∆E. Two factors contribute to broadening of a spectral line.
Doppler Effect and molecular collisions. The Doppler shifting of frequencies at which the
molecules experience the incident radiation by virtue of their random motions toward or
away from the source of the radiation, and. pressure broadening: associated with molecular
collisions.

IR spectroscopy
Vibrational spectroscopy is due to the interaction of matter with the Infrared region of the
electromagnetic spectrum.
Spectral Range of IR Radiation:
• Near IR: 12000 cm-1 to 4000 cm-1
• MID IR: 4000 cm-1 to 620 cm-1
• Far IR: 300 cm-1 to 10 cm-1
The mid-IR region is used for the sample analysis in IR spectroscopy.
Quantum Approach

Irradiation of samples with IR radiation brings about vibrational changes in molecules. The
transition of molecules is from a lower vibrational energy level to a higher vibrational energy
level. The transition is induced by the absorption of photons of the IR radiation of appropriate
frequency, which matches with energy gap between the two levels.
IR absorption by molecules happens only when there is a change in the dipole moment of the
molecule.
Dipole Moment (µ) = Charge (Q) * distance of separation (r)
(Measured in Debye units denoted by ‘D’. 1 D = 3.33564 × 10-30 Cm, where C is Coulomb
and m is meter)
The bond dipole moment that arises in a chemical bond between two atoms of different
electronegativities can be expressed as follows:
μ = 𝛿.d
where μ is the bond dipole moment, 𝛿 is the magnitude of the partial charges 𝛿 + and 𝛿 –
and d is the internuclear distance between 𝛿 + and 𝛿 – .
The bond between the atoms is considered as a spring that can undergo stretching and
bending vibrations. During vibration, there is a change in the dipole moment of the molecule
as a result of the change in the distance between the atoms. When an atom in a molecule is
stretched over a certain distance keeping the other atom stationary, the atom gets displaced
from its equilibrium position by distance “x”. To attain equilibrium, the atom tries to move
back to the original position, by applying a restoring force that is equal to the displaced
distance but will be in the opposite direction and has a negative value.
According to Hook’s Law: -restoring force α x
-F α x or -F = kx, k = force constant
The modes of stretching and bending
The simplest types, or modes, of vibrational motion in a molecule that are infrared active—
those, that give rise to absorptions—is the stretching and bending modes
 Instrumentation

Different parts of FTIR instrumentation include:

1. The Source: A broadband emitter, such as a mid-IR ceramic source, a far-infrared mercury
lamp, or a near-infrared halogen lamp, Globar etc.. is used as the light source.
2. The Interferometer (Michelson) The interferometer, which consists of a beamsplitter, a
stationary mirror, and a moving mirror (heart of an FTIR spectrometer). The beamsplitter is a
semi-transparent mirror that divides a collimated light beam into two optical channels. Half
of the light is transferred to the moving mirror and half is reflected to the stationary mirror.
 The moving and stationary mirrors reflect the two light beams, which are recombined at the
beamsplitter before going through the sample chamber and onto the detector.
3. The Sample: NaCl or KBr -The beam enters the sample compartment where it is transmitted
through or reflected off of the surface of the sample, depending on the type of analysis being
accomplished. This is where specific frequencies of energy, which are uniquely characteristic
of the sample, are absorbed.
4. Detector FTIR detectors are used to measure and convert the transmitted or reflected light
from a sample into an electrical signal. The detectors used are specially designed to measure
the special interferogram signal. Ex : Pyro electric detectpr is a regular analysis tool.
5. The Computer: The measured signal is digitized and sent to the computer where the Fourier
transformation takes place. The final infrared spectrum is then presented to the user for
interpretation and any further manipulation.

Principle of FTIR
The Michelson interferometer consists of a beam splitter, a moving mirror, and a stationary
mirror. The beam splitter divides the light beam into two halves, which are reflected by the
moving and fixed mirrors before being recombined by the beam splitter.
As the moving mirror makes reciprocating movements, the optical path difference to the
fixed mirror changes, causing the phase difference to shift over time. Interference light is
created in the Michelson interferometer by recombining the light beams. An interferogram
records the intensity of the interference light, with the optical path difference recorded along
the horizontal axis.

Working
The FT-IR uses an interferometer to process the energy sent to the sample. In the
interferometer, the source energy passes through a beam splitter, a mirror placed at a 45°
angle to the incoming radiation, which allows the incoming radiation to pass through but
separates it into two perpendicular beams, one undeflected, the other-oriented at a 90° angle.
One beam, the one oriented at 90° in Figure, goes to a stationary or “fixed” mirror and is
returned to the beam splitter. The undeflected beam goes to a moving mirror and is also
returned to the beam splitter. When the two beams meet at the beam splitter, they recombine,
but the pathlength differences (differing wavelength content) of the two beams cause both
constructive and destructive interferences.
 The interferogram generated by combining the two beams is oriented toward the
sample. As it passes through the sample, the sample simultaneously absorbs all of the
wavelengths (frequencies) that are normally found in its infrared spectrum. The modified
interferogram signal that reaches the detector contains information about the amount of ene
rgy that was absorbed at every wavelength (frequency).
The design of the optical pathway produces a pattern called an interferogram. It's a plot of
intensity vs. Time later transformed to plot of intensity vs. frequency

Advantages of FTIR
 It has a higher speed. Because all of the frequencies are detected simultaneously,
 It has high sensitivity with higher optical throughput, resulting in much lower noise levels.
 It is a very accurate and reproducible method.
 It is an extremely reliable approach for positively identifying almost any material.
 It can be used to capture IR data from very small samples.
 The radiant power reaching the detector is significantly higher than in a dispersive device.
 It has high precision. The laser in an FT-IR spectrometer serves as the instrument’s reference
signal and timekeeper. It also moves at the same rate as other components inside its own
system. This can provide reliable measurements without being influenced by outside sources
such as sunlight or temperature fluctuations.

Limitations
 The molecule must be active in the infrared range. (When exposed to IR radiation, a
minimum of one vibrational motion must change the molecule’s net dipole moment for
absorption to be noticed.)
 For the majority of samples, minimal elemental information is provided.
 The material being tested must be transparent in the spectral region of interest.

Regions of IR spectrum
Selection rules for Infrared transitions
For a particular vibration to be infrared active there must be a change in the dipole moment of
the molecule during the vibration.
Homonuclear diatomic molecules are inactive in the infrared spectrum. eg: H2, O2, N2 etc
Heteronuclear diatomic molecules such as CO, NO are active in IR.
Symmetrical polyatomic molecules such as CO2, the symmetric stretching vibration is
infrared inactive where as the asymmetric stretching vibration is IR active ∆ν = ± 1, transition
can take place between Adjacent vibrational levels, 0 to 1, 1 to 2, etc.
• IR spectrum shows bands rather than line spectrum due to the coupling of various
rotational transitions within a given vibrational transition.

Applications of IR spectroscopy
As two molecules of different structure don’t have exactly the same infrared absorption
pattern. Thus, the infrared spectrum can be used for molecules much as a fingerprint.
The infrared spectrum is to determine structural information about a molecule. The
absorptions of each type of bond (N-H, C-H, O-H, C-X, C-O, C=O, C-C, C=C, C≡C, C≡N,
and so on)
Prediction of an Organic molecule
Cyclohexane

3-methyl 2-butanone

2 marks
 Width and Intensity of Spectral Lines
 Modes of Vibrations
 Regions in IR spectra
6-8 marks
 Construction and working of FTIR – Instrumentation
 Hooks law numerical
 Advantages and disadvantages of FTIR