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RAMAN

SPECTROSCOPY

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Definition
• Raman spectroscopy belongs
into the category of vibrational
spectroscopy. This means that
it analyzes a sample chemically,
by using light to create (excite)
molecular vibration, and
interpreting this interaction
afterwards.

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RAMAN EFFECT
• It is based on the inelastic scattering of light that occurs when matter
is irradiated by light. As the change of wavelength is very small
compared to the wavelength of the irradiating light, the change of
wavelength is most easily observed when using monochromatic light
sources.
• After this (monochromatic) light has interacted with the sample, a
very small part of it has changed its wavelength. This is change is
called: the Raman effect. We can now collect that light and can use it
to gain information about the sample.

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RAMAN EFFECT
• For analysis of molecular structure – complimentary to infrared spectroscopy.
• Raman effect – scattering of light, which includes elastic scattering at the same
wavelength as the incident light and inelastic scattering at different wavelengths,
due to molecular vibrations.

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RAMAN EFFECT
• Raman spectra are measured by exciting a sample using a high-
intensity laser beam, with the resulting scattered light being passed
through a spectrometer.

• Raman shift is the energy difference between the incident light and
the scattered light.

• In the resulting spectrum, the vertical axis is the intensity of the


scattered light and the horizontal axis is the wavenumber of the
Raman shift.

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RAMAN SHIFT
• Associated with two different energy
bands.

• The shift at wavelengths higher than that


of the incident light – STOKES scattering.

• The shift at wavelengths lower than that of


the incident light – ANTI-STOKES
scattering.

• Stokes scattering is observed in the lower


wavenumber [Longer wavelength] region
and anti-stokes scattering in the higher
wavenumber [shorter wavelength] region. 6
Difference between RAMAN and IR
• IR is based on absorption of light energy corresponding to the vibrational energy
of molecules.
• Raman spectroscopy is based on scattering of incident light at an energy shifted
by the vibrational energy [hv] of the molecule.
• Vibration modes for the same functional groups are observed at the same
wavenumber.

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Difference between RAMAN and IR
• IR spectroscopy is based on the fact that molecular absorption at
specific vibrational frequencies causes in the polarizability of a
molecule at the frequencies at which the molecule scatters radiation.

• IR is sensitive to hetero-nuclear functional group vibrations and polar


bonds [OH stretching in water]

• Raman is sensitive to homo-nuclear molecular bonds such C-C, C=C


and C≡C bonds.

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Advantages of RS
• Used for depth profiling and microscopic area mapping of samples
with a spatial resolution of around 1µm.

• Optical fibers with remote probes can be used for sensitive in-situ
analysis.

• Measurements can be performed on opaque or cloudy samples, and


directly through glass or plastic containers, making sample
preparation much simpler.

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Applications
Field Applications
Light stability of ciprofloxacin tablets, xanthine derivative tablets, quinolone delivative
antibacterial tablets, theophylline hydrates, anhydrates, crystalline polymorphs of
indomethacin, crystalline polymorphs of carbamazepine (CBZ), crystalline polymorphs of
Pharmaceuticals ampicillin, crystal structure and thermal stability of acetylsalicylic acid (aspirin), active
ingredients in drug substances and their preparation (Jpn Pharmacopeia),
qualitative/quantitative evaluation of additives (Jpn Pharmacopeia), bronchodilator (TBR,
turobuterol) tape
Component distribution on white chocolate surface, butter/margarine emulsion imaging ,
components of egg yolk, thermal change of trehalose dihydrate, fatty acid in food oil,
Foods aaccharides solutions (saccharose, glucose, xylitol, galactose, lactose), multilayer films for food
packaging, ethanol in glass bottles, caffeine, crystallinity of PET bottles
Carbon materials Carbon nanotubes, diamond-like carbon, fullerenes
Semiconductors Power semiconductor (SiC) devices, crystallinity of polysilicon
Electronic Foreign matter in liquid crystal substrates, foreign matter in color filters, diamond-like carbon
devices on hard disk surfaces, solar cells (crystalline silicon, amorphous silicon) 10
Applications
Field Applications

3D imaging of cellophane tape, polypropylene-polyethylene multilayer films,foreign


Polymer matter on polyethylene films, polymer additives, dispersion in blended polymers,
compounds crystallization of molten polymers, curing of UV curable resin, dispersion of lubricant
on films, orientation of natural rubber, synthetic rubber

Visualization of sea-island structure in blended polymers, structural changes in


Biological proteins (hemoglobin, lysozyme, cytochrome c), enzymes (ribonuclease A), dental
materials adhesive, collagen, chemical imaging of coral, structure and orientation evaluation of
spider silk
Cosmetics Ingredients of lipstick marks, eye shadow
Gas Natural gas hydrates
Imaging of bath powder (mixed powder samples), carbon nanotubes, crystallinity of
core of pencils, identification of fingerprints with vermilion ink, iron rust, colored
Others fibers, Nylon 6 fibers, wood (lignin), quartz, calcite, nondestructive analysis of
archaeological material (mainly pigments) 11
RAMAN IMAGING
• Is a powerful technique that provides 3-D spatial information and
chemical identification.
• Samples with dimensions of micrometers to millimeters can be
analyzed in just a few minutes.

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THANK YOU

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