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Very Basic Overview: Raman Spectros

Raman spectroscopy is a technique that uses laser light to study vibrational and rotational modes in a system. [1] It can be used to obtain a molecular fingerprint to identify materials. [2] Raman spectroscopy provides advantages over infrared spectroscopy such as not requiring water-sensitive sample preparation and being able to analyze samples in solution. [3] It is commonly used to analyze pharmaceuticals, minerals, and other materials.
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0% found this document useful (0 votes)
75 views18 pages

Very Basic Overview: Raman Spectros

Raman spectroscopy is a technique that uses laser light to study vibrational and rotational modes in a system. [1] It can be used to obtain a molecular fingerprint to identify materials. [2] Raman spectroscopy provides advantages over infrared spectroscopy such as not requiring water-sensitive sample preparation and being able to analyze samples in solution. [3] It is commonly used to analyze pharmaceuticals, minerals, and other materials.
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Raman Spectroscopy

Very Basic Overview

Arif Hindarto
Halley Rionanda
30 Agustus 2019
Raman Spectroscopy

A Historical Perspective
What is Raman Spectroscopy?
Theoretical Principles
Analytical Applications
Advantages and Disadvantages
Why use Raman spectroscopy?
Raman Spectroscopy

Sir Chandrasekhara
Venkata Raman
1930 Nobel Physics

Investigations of the Raman Effect began in many


countries in 1930’s
History of Raman Spectroscopy
1928 - First experiments with light scattering by C. V. Raman
using sunlight as source
1930's - mercury arc lamps and photographic film used to
capture spectra. Raman is the spectroscopic technique of
choice
1950’s - Cheaper IR technique overtakes Raman
1960's - gas lasers and photo-multiplier (PMT) detectors available
for collection of Raman spectra
1980's - diode array detectors are used
1990's - FT-Raman instruments commercially available
Present day: solid state lasers, Peltier cooled CCD detectors….
Spektroskopi = ilmu yang mempelajari materi dan attributnya berdasarkan cahaya,
suara, atau partikel yang dipancarkan, diserap, atau dipantulkan oleh materi tersebut
C. V. Raman’s Experiment

Sunlight- Scattering
Filters Observer
via telescope sample

• Sunlight passed through coloured filters


• Complementary filters extinguish beam completely

• No light is seen by observer


C. V. Raman’s Experiment
Sunlight- Scattering
Filter Filter Observer
via telescope sample

• Yellow filter moved to after the scattering sample


• Some light is red-shifted by the sample
• Yellow filter now allows some light to be seen

• Some light was inelastically scattered by the molecules


(“Raman”scattering)
Vibrational Spectroscopy

Absorption

Scattering (“emission”)

A molecule can be characterised (or identified) based


on the wavelength and intensity of the spectral peaks.
Simple Raman Spectrograph

Sample Spectrograph
Laser

Detector

Laser / Rayleigh
Rejection notch filter (10-4 ~ 10-6)
Laser (Light Amplification by Stimulated Emission of Radiation) merupakan
mekanisme suatu alat yang memancarkan radiasi elektromagnetik, biasanya
dalam bentuk cahaya yang tidak dapat dilihat maupun dapat lihat dengan mata
normal, melalui proses pancaran terstimulasi.
The Raman Spectrum
Intensity

Excitation n0

Stokes
Anti-Stokes
(n0 -n1)
(n0 +n1)

0 Raman shift in cm-1 (“Kaisers”)


The Raman Spectrum
CCl4
Stokes anti-Stokes

Decreasing absolute wavenumber

Red Blue

The 'complete' Raman spectrum contains both the red-shifted Stokes and blue-shifted
anti-Stokes scattering. Normally we only collect the Stokes peaks as they are more
intense. Note the strong attenuation of the laser / Rayleigh scattering.
Comparison of Raman and Infrared
Sample preparation for infrared spectroscopy is critical and often tedious.
There is generally no sample preparation for micro-Raman samples.
Infrared samples require fragile, water-sensitive sample cells or complex,
expensive sampling accessories with limited spectral ranges.
Raman samples are placed in the path of the laser.
Water is a nuisance for most infrared analyses.
Water is an ideal solvent for Raman sampling, with a very weak
interference.
Infrared quantitation can approach ppm levels for some samples and
even ppb levels for gases, but most samples are limited to detection
levels in the 0.01 to 0.001% range.
Raman spectra can be used for quantitation with a detection limit
approaching 0.01% in some cases. But only TINY amounts of sample
needed!
Raman Sampling Advantages
• Simple sample preparation / No sample preparation
• Depth profiling and microscopic mapping of samples with spatial resolution
approaching 1 micron
• Quartz optical fibres used for in-situ analysis, remote probes
• No combinations or overtones, less 'clutter' in Raman spectra
• No water sensitive or range limiting optics, cells or accessories
• A complete spectrum is collected, from >4,000 to ~50 cm-1 or less
• Opaque or cloudy samples OK
• Sample containers can be glass or plastic and sample in-situ
Sampling Configurations
360 degree transmission
Macro
Micro
Macro

45 degree
pseudo-backscattering

Macro

Micro

90 degree backscattering 180 degree backscattering


Old vs New: Spectrographs

PMT
slit slit
scanned grating

scanned grating
(1 or 2 required) slit

The old way: 2 or 3 gratings and PMT detector

Slit = Celah
Old vs New: Spectrographs

slit
slit
CCD
notch
filter Grating is set to 1
or more positions

Each grating position


generates a broad spectrum

The new way: notch filter, 1 grating and CCD detector


PMT = Photo-multiplier, hanya dapat membaca 1 panjang gelombang pada waktu
yang sama
CCD = Charge couple device, membaca large number of light
Raman Sampling Disadvantages

• More expensive technique comparing to IR spectroscopy


• Raman spectroscopy alone is not a very sensitive technique compared with IR
• High powered lasers and amplification sources are needed to get sensitive
results
• The heating of samples through the intense laser radiation can also destroy the
sample or cover the Raman spectrum
Application (Kegunaan)

• Pharmaceuticals and Cosmetics


• Geology and Mineralogy
 Gemstone and mineral identification
 Fluid inclusions
 Mineral and phase distribution in rock sections
 Phase transitions
 Mineral behaviour under extreme conditions

Raman spectra of (top to bottom)


olivine, apatite, garnet and gypsum
illustrating how Raman can be used
for fast mineral ID
Selesai,,,
Terima Kasih,,,

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