IR and FT-IR Spectroscopy

• IR radiation is used to investigate vibrational level of molecules

• Usual range ( 10 – 4000 cm-1) ...convert into eV ..energy scale , and also nm, wavelength
• Simple case a diatomic molecule ...in a harmonic motion ..mass and spring type
• In a simplistic approach, the frequency of vibration can be estimated using harmonic
potential model
• En = (n + 1/2) hν , n = 0, 1, 2,.....,
• In reality , anharmonic oscillator model
works in which energy levels are NOT
equally spaced
• En = (n + ½)2 hv - (hv/De )(n + ½)2
• De is the Ionisation potential
 EM Spectra and IR position

https://www.open.edu/openlearn/mod/oucontent/view.php?id=83459&section=2.2
 Dipole Moment – what and why is important?

• In order to have IR activity , the molecule MUST have a CHANGE in the Dipole moment
• A molecule can vibrate in many ways, and each way is called a vibrational mode. For
molecules with N number of atoms, geometrically linear molecules have 3N – 5 degrees of
vibrational modes, whereas nonlinear molecules have 3N – 6 degrees of vibrational modes
(also called vibrational degrees of freedom). As examples linear carbon dioxide (CO2) has
3 × 3 – 5 = 4, while non-linear water (H2O), has only 3 × 3 – 6 = 3.
 Infrared Source and Detectors
• Sources : any kind of filament lamp that emit a large IR radiation
• Detectors: Thermocouple, Bolometer, Thermistor, Golay cell, Pyroelectric, and Semiconductor detector
Thermocouple: A metallic junction, which produces a voltage across two free ends when exposed to
temperature
Bolometer : Electronic device that detects IR radiation by measuring temperature dependent electrical
resistance of materials
Thermistor: Resistance depends on temperature
Golay cell: The Golay cell is a type of opto-acoustic detector mainly used for infrared spectroscopy. It consists of
a gas-filled enclosure with an infrared absorbing material and a flexible diaphragm or membrane. When
infrared radiation is absorbed, it heats the gas, causing it to expand. The resulting increase in pressure deforms
the membrane. Light reflected off the membrane is detected by a photodiode, and motion of the membrane
produces a change in the signal on the photodiode

Pyroelectric detector: Materials develop voltage across opposite faces when heated
Semiconductor detector: Mercury Cadmium Telluride (HgCdTe) alloy semiconductor
 Vibrational Frequency of HCl molecule
Q. The HCl equilibrium bond length is 0.127 nm and the v=0 to v=1 transition is observed in the infrared at 2,886 cm-1. Compute the vibrational energy of
HCl in its lowest state. Compute the classical limit for the stretching of the HCl bond from its equilibrium length in this state. What percent of the equilibrium
bond length is this extension

• A. H-Cl bond length = 0.127nm = 1.27 * 10^-10m

• Transition observed at 2886 cm^-1 => 2886 cm^-1 * (3*10^10 cm/s) = 8.646*10^13 s^-1 or 8.656*10^13 Hz
• Ev = (v + 1/2)(hbar)(w), or, at v=0 (ground state), E0 = (1/2)(hbar)(w)
• The term w (omega) is equal to sqrt(k/u) where k is the force constant of the molecular bond and u is the reduced mass of the molecule.
• Reduced mass = m1m2/(m1+m2) or ~ (17)(1)/(17+1) amu
• or when converted into kg, is 1.568*10^-27kg
• The term w is also equal to 2(pi)(f), so we can solve for k by the equality 2(pi)(f) = sqrt(k/u) or
• 2(pi)(8.656*10^-13 Hz) = sqrt(k/(1.57*10^-27 kg)) where we obtain k = 481 N/m
• and w = sqrt((481 N/m)/1.57*10^27 kg)) = 5.54*10^14 rad/s
• We can then acquire the ground state vibrational energy from
• E0 = (1/2)(hbar)(w) = (1/2)(hbar)(5/54*10^14 rad/s) = 2.916*10^-20 J
• The classical limit of the stretch is denoted as Q0, this can be equated as potential energy in relation to the total E0 found above as, at E0, all of the energy
would be potential energy in the form of the stretch. In comparison to the classic spring force equation, Q0 is calculated as V = (1/2)(k)(Q0^2)
• As described above, we can relate the two as (1/2)(hbar)(w) = (1/2)(k)(Q0^2)
• or, 2.916*10^-20 J = (1/2)(481)(Q0^2) where Q0 = 1.10*10^-11 m or 0.0110 nm
• Lastly, this classical limit to length can be compared to the equilibrium bond length by a simple relation of
• (Q0/xeq)*100 = Percent bond length => (0.110nm)/(0.127nm)*100 = 8.66%
 Fourier Transform Spectrometer

• Double beam interference based spectroscopy

• Basic design similar to that of Michelson Interferometer
• A movable mirror introduces variable optical path difference in one of the beams
• I (x) = ∫ I(ν) Cos(2πx ν) dν is the distribution of the signal with mirror movement x and is recorded
• This is converted into I (ν) = ∫ I(x) Cos(2πx ν) dx as the final output through Fourier transform
Modified Optical Design
 Raman Spectroscopy
Rayleigh Scattering
1.The molecule is excited to any virtual state.
2.The molecule relaxes back to its original state.
3.The photon is scattered elastically, leaving with its original
energy.
Stokes Scattering
1.The molecule is excited to any virtual state.
2.The molecule relaxes back to a higher vibrational state than it
had originally.
3.The photon leaves with energy hν-ΔE and has been scattered
inelastically.
Anti-Stokes Scattering
1.The molecule begins in a vibrationally excited state.
2.The molecule is excited to any virtual state.
3.The molecule relaxes back to a lower vibrational state than it
had originally.
4.The photon leaves with energy hν+ΔE, and has been
scattered superelastically.

https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Physical_Methods_in_Chemistry_and_Nano_Science_(Barron)
/04%3A_Chemical_Speciation/4.03%3A_Raman_Spectroscopy
 Raman spectroscopy
Raman spectroscopy is a powerful tool for determining chemical species. As with other spectroscopic techniques, Raman
spectroscopy detects certain interactions of light with matter. In particular, this technique exploits the existence of Stokes and
Anti-Stokes scattering to examine molecular structure. When radiation in the near infrared (NIR) or visible range interacts
with a molecule, several types of scattering can occur. Three of these can be seen in the energy diagram
In all three types of scattering, an incident photon of energy hν raises the molecule from a vibrational state to one of the
infinite number of virtual states located between the ground and first electronic states. The type of scattering observed is
dependent on how the molecule relaxes after excitation.
Rayleigh scattering is by far the most common transition, due to the fact that no change has to occur in the vibrational state
of the molecule. The anti-Stokes transition is the least common, as it requires the molecule to be in a vibrationally excited
state before the photon is incident upon it. Due to the lack of intensity of the anti-Stokes signal and filtering requirements
that eliminate photons with incident energy and higher, generally only Stokes scattering is used in Raman measurements. The
relative intensities of Rayleigh, Stokes and anti-Stokes scattering can be seen in Figure
 Raman and IR – Differences
Raman spectroscopy observes the change in energy between the incident and scattered photons associated with the Stokes and
anti-Stokes transitions. This is typically measured as the change in the wavenumber (cm-1), from the incident light source.
Because Raman measures the change in wavenumber, measurements can be taken using a source at any wavelength; however,
near infrared and visible radiation are commonly used. Photons with ultraviolet wavelengths could work as well, but tend to
cause photodecomposition of the sample.
Comparison between Raman and Infrared Spectroscopy
Raman spectroscopy sounds very much like infrared (IR) spectroscopy; however, IR examines the wavenumber at which a
functional group has a vibrational mode, while Raman observes the shift in vibration from an incident source. The Raman
frequency shift is identical to the IR peak frequency for a given molecule or functional group. As mentioned above, this shift is
independent of the excitation wavelength, giving versatility to the design and applicability of Raman instruments.
The cause of the vibration is also mechanistically different between IR and Raman. This is because the two operate on different
sets of selection rules. IR absorption requires a dipole moment or change in charge distribution to be associated with the
vibrational mode. Only then can photons of the same energy as the vibrational state of molecule interact. A schematic of this can
be seen in Figure

Raman signals, on the other hand, due to scattering, occur because of a molecule’s polarizability, illustrated in Figure above.
Many molecules that are inactive or weak in the IR will have intense Raman signals. This results in often complementary
techniques
 Scattering Process
When light interacts with molecules in a gas, liquid, or solid, the vast majority of the photons are dispersed at the same
energy as the incident photons. This is described as elastic or Rayleigh scattering. A small number of these photons,
approximately 1 photon in 10 million will disperse at a different frequency than the incident photon. This process is called
inelastic scattering, or the Raman effect, named after Sir C.V. Raman who discovered this and was awarded the 1930 Nobel
Prize in Physics for his work. Since that time, Raman has been utilized for a vast array of applications from medical
diagnostics to material science and reaction analysis. Raman allows the user to collect the vibrational signature of a
molecule, giving insight into how it is put together, as well as how it interacts with other molecules around it.

Unlike FTIR Spectroscopy that looks at changes in dipole moments, Raman looks at changes in a molecular bonds
polarizability. Interaction of light with a molecule can induce a deformation of its electron cloud. This deformation is
known as a change in polarizability. Molecular bonds have specific energy transitions in which a change of polarizability
occurs, giving rise to Raman active modes. As an example, molecules that contain bonds between homonuclear atoms
such as carbon-carbon, sulfur-sulfur, and nitrogen-nitrogen bonds undergo a change in polarizability when photons
interact with them. These are examples of bonds that give rise to Raman active spectral bands, but would not be seen or
difficult to see in FTIR.
Because Raman is an inherently weak effect, the optical components of a Raman Spectrometer must be well matched
and optimized. Also, since organic molecules may have a greater tendency to fluoresce when shorter wavelength
radiation is used, longer wavelength monochromatic excitation sources, such as solid state laser diodes that produces
light at 785 nm, are typically used.
https://www.mt.com/in/en/home/applications/L1_AutoChem_Applications/Raman-Spectroscopy.html
 How to choose?
Choose Raman Spectroscopy when:
•Investigating carbon bonds in aliphatic and aromatic rings are of primary interest
•Bonds that are difficult to see in FTIR (i.e., 0-0, S-H, C=S, N=N, C=C etc.)
•Examination of particles in solution is important, e.g. polymorphism
•Lower frequency modes are important (e.g. Inorganic-Oxides)
•Reactions in aqueous media are investigated
•Reactions in which observation through a reaction window is easier and safer (e.g. high pressure catalytic
reactions, polymerizations)
•Investigating lower frequency lattice modes is of interest
•Investigation of reaction initiation, endpoint, and product stability of biphasic and colloidal reactions

Choose FTIR Spectroscopy when:

•Studying liquid-phase reactions
•Reactions in which reactants, reagents, solvents and reaction species fluoresce
•Bonds with strong dipole changes are important (e.g. C=O, O-H, N=O)
•Reactions in which reagents and reactants are at low concentration
•Reactions in which solvent bands are strong in Raman and can swamp key species signal
•Reactions in which intermediates that form are IR active
An example of Raman spectra

Raman spectrum of HiPco SWNTs using a laser of wavelength of λexc = 633 nm. Adapted from R. Graupner, J. Raman Spectrosc.,
2007, 38, 673.