Instrumental Analysis

(Raman spectroscopy)

Young Gyu Jeong

Department of Organic Materials Engineering
Chungnam National University

Chap 18.
Raman Spectroscopy

 Theory of Raman Spectrometry

 Instrumentation
 Applications of Raman Spectroscopy
 Other Types of Raman Spectroscopy

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  Raman spectroscopy
 The visible wavelength of a small fraction of the radiation scattered by certain molecules differs from
that of the incident beam and furthermore that the shifts in wavelength depend on the chemical
structure of the molecules responsible for the scattering  C. V. Raman (1931 Nobel Prize in physics)
 Raman scattering results from the same type of quantized vibrational changes associated with IR
absorption.
 The difference in wavelength between the incident and scattered visible radiation corresponds to
wavelengths in the mid-IR region.

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Theory of Raman Spectroscopy

 Advantages of Raman spectroscopy

 Water can be a quite useful solvent
 Glass or quartz cells can be employed, because signals are usually in the visible or near-IR region

 Disadvantages of Raman spectroscopy

 Not widely used until lasers became available in the 1960s
 Signals are Interrupted by fluorescence of samples or impurities in samples
 To avoid fluorescence, the excitation wavelengths are usually well removed from an absorption band
of the analyte

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 Theory of Raman Spectroscopy

Figure 6-18 Inelastic scattering in Raman spectroscopy.

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Theory of Raman Spectroscopy

Excitation of Raman spectra

 Argon ion laser: 488.0 nm

 Stokes scattering
 Anti-Stokes scattering
 Rayleigh scattering
 Wavenumber shift

Figure 18-1 The origin of Raman spectra. In (a) radiation from a source that is incident
on the sample produces scattering at all angles. The incident radiation causes excitation
(a) to a virtual level j and subsequent reemission of a photon of lower (left) or higher
(right) energy. The Raman spectrum (b) consists of lower-frequency emissions called
Stokes scattering and higher-frequency emissions termed anti-Stokes scattering.

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 Theory of Raman Spectroscopy
Mechanisms of Raman and Rayleigh scattering

Rayleigh

Stokes Anti-Stokes
Intensity

Raman shift, cm-1

Figure 18-2 Raman spectrum of CCl4, excited by laser

radiation of ex = 488 nm.

Figure 18-3 Origins of Rayleigh and Raman scattering.

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Theory of Raman Spectroscopy

Wave model of Raman and Rayleigh scattering
 Electric field of a radiation beam: E  E0 cos  2 vex t 
 Induced dipole moment
of an analyte bond: m   E   E0 cos  2 vex t 

Polarizability of the bond

   0 : The polarizability of the bond

   0   r  req    at the equilibrium
 r  internuclear distance req
r  req  rm cos  2 vvt  r : The internuclear separation
at any instant
  rm : The maximum internuclear
   0    rm cos  2 vvt  separation relative to the
 r 
equilibrium position

   cos( x  y )  cos( x  y )
m   0 E0 cos  2 vex t   E0 rm   cos  2 vvt  cos  2 vex t  cos x cos y 
 r  2

E0    E0   
m   0 E0 cos  2 vex t   rm   cos  2  vex  vv  t   rm   cos  2  vex  vv  t 
2  r  2  r 
Rayleigh scattering Stokes scattering Anti-Stokes scattering

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 Theory of Raman Spectroscopy
Wave model of Raman and Rayleigh scattering
 Infrared absorption spectroscopy
 There be a change in dipole moment or charge distribution during the vibration
 Only radiation of the same frequency can interact with the molecule and promote it to an excited
vibrational state

 Raman scattering spectroscopy

 It involves a momentary distortion of the electrons distributed around a bond in a molecule, followed by
reemission of the radiation as the bond returns to its normal state
 In the distorted form, the molecule is temporarily polarized; that is, it develops momentarily an induced
dipole that disappears on relaxation and reemission
 The polarizability of the bond between the two atoms of such a molecule varies periodically in phase
with the stretching vibrations, reaching a maximum at the greatest separation and a minimum at the
closest approach
 A Raman shift corresponding in frequency to that of the vibrational mode results

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Theory of Raman Spectroscopy

Wave model of Raman and Rayleigh scattering
 Comparison of the IR and the Raman activities of coupled vibrational modes
 Symmetric and asymmetric vibrational modes of CO2:

Infrared inactive Infrared active

Raman active Raman inactive

expanded equilibrium compressed

O C O O C O O C O

Polarizability
ellipsoid

 IR and Raman spectroscopy: mutual exclusion principle

 Parts of Raman and IR spectra are complementary

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 Theory of Raman Spectroscopy
Wave model of Raman and Rayleigh scattering

 In case of IR absorption spectroscopy:

Example 1) C=O vibration of CO2 Example 2) H2O, CS2, NO2

Inactive 2330 cm-1

3650 cm-1

677 cm-1 (degenerate) 3760 cm-1 1595 cm-1

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Theory of Raman Spectroscopy

Wave model of Raman and Rayleigh scattering
 IR absorption and Raman scattering spectra

Figure 18-3 Comparison of Raman and IR spectra for mesitylene and indene.

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 Theory of Raman Spectroscopy
Wave model of Raman and Rayleigh scattering
 IR absorption and Raman scattering spectra

PDMS : Polydimethylsiloxane

Sym Si-O-Si stretch

CH3

Si O
(a. u.)

Sym Si-C stretch

n
CH3
or Absorbance

Asym Si-C stretch

(a.u.)

Raman
Intensity Intensity

Asym Si-O-Si stretch

vs.
Infrared

500 1000 1500 2000 2500 3000 3500

Wavenumber (cm-1)

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Theory of Raman Spectroscopy

Intensity of normal Raman bands
 Factors influencing the intensity or radiant power of a normal Raman band
 the polarizability of the molecule
 the intensity of the source
 the concentration of the active group
 other factors

 In the absence of absorption, the power of Raman emission increases with the fourth power of the
frequency of the source

 Raman intensities are usually directly proportional to the concentration of the active species. In this
regard, Raman spectroscopy more closely resembles fluorescence than absorption, in which the
concentration intensity relationship is logarithmic

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 Theory of Raman Spectroscopy
Raman depolarization ratios
 Depolarization ratio
 It is sometimes useful in determining
the structure of molecules, in addition
to intensity and frequency information

 Polarizability
 a molecular property having to do
with the deformability of a bond

 Polarization
 a property of a beam of radiation
 It describes the plane in which the
radiation vibrates

Figure 18-5 Depolarization resulting from Raman scattering.

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Instrumentation
Sources

Figure 18-6 Block diagram of a Raman spectrometer. The laser radiation is

directed into a sample cell. The Raman scattering is usually measured at right
angles to avoid viewing the source radiation. A wavelength selector isolates the
desired spectral region. The transducer converts the Raman signal into a
proportional electrical signal that is processed by the computer data system.

 Two major advantages of near-IR sources

 They can be operated at much higher power (up
to 50 W) without causing photodecomposition of
the sample
 They are not energetic enough to populate a
significant number of fluorescence-producing
excited electronic energy states in most Raman shift, cm-1
molecules
Figure 18-7 Spectra of anthracene taken with a
 Nd-YAG laser (1064 nm) conventional Raman instrument with an argon-ion
Diode laser at 785 and 830 nm laser source at 514.5 nm (A) and with an FT-Raman
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 Instrumentation
Sample-illumination system

 Gas samples

 Liquid samples

 Solid samples

Figure 18-8 Sample illumination systems for Raman spectrometry. In (a), a gas cell is shown
with external mirrors for passing the laser beam through the sample multiple times. Liquid cells
can be capillaries (b) or cylindrical cell (c). Solids can be determined as powders packed in
capillaries or as KBR pellets (d).

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Instrumentation
Fiber-optic sampling
Relative intensity

Raman shift, cm-1

Figure 18-10 Raman spectrum of an aqueous solution

containing aprotinin (100 mg/mL) and (NH4)2SO4 (1.0 M) in
50 mM sodium acetate buffer at pH 4.5 and 24 oC. A diode
Figure 18-9 Raman spectrometer with fiber-optic probe.
laser at 785 nm was used with a CCD detector.

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 Instrumentation
Raman microprobe
 Raman microscope

 Confocal Laser Raman Spectrometer  633 nm He-Ne laser

 Spatial resolution: 1 m (lateral) and 2 m (axial)

 spatial (lateral) resolution

 spatial (axial or depth) resolution

  /(na) 2

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Instrumentation
Raman spectrometers
 Wavelength-selection devices and transducers

Figure 18-11 Fiber-optic Raman spectrometer with spectrograph and CCD detector.
The bandpass filter (BP) is used to isolate a single laser line. The band-rejection
(BR) minimizes the Rayleigh-scattered radiation.

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 Instrumentation
Raman spectrometers
 Fourier transform Raman spectrometers

Figure 18-12 Optical diagram of an FT-Raman instrument. The laser radiation passes through the
sample and then into the interferometer, consisting of the beam-splitter and the fixed and movable
mirrors. The output of the interferometer is then extensively filtered to remove stray laser radiation and
Rayleigh scattering. After passing through the filters, the radiation is focused onto a cooled Ge detector.
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Applications of Raman spectroscopy

 Raman spectra of inorganic species

 They are often superior to IR spectroscopy for investigating inorganic systems because aqueous
solutions can usually be employed
 The vibrational energies of metal-ligand bonds are generally in the range of 100 to 700 cm-1

 Raman spectra of organic species

 They are similar to IR spectra in that they have regions useful for functional group detection and
fingerprint regions that permit the identification of specific compounds
 Raman spectra yield more information about certain types of organic compounds with double-bond
stretching vibration for olefins

 Biological applications of Raman spectroscopy

 It has been widely applied for the study of biological systems
 Advantages: the small sample requirement, the minimal sensitivity to water, the spectral detail, and the
conformation and environmental sensitivity

 Quantitative applications
 Raman spectra tend to be less cluttered with bands than IR spectra
 Not interfered by small amounts of water in a sample
 An image of regions on a surface can be obtained

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 Applications of Raman spectroscopy

 Structural analysis of polymer blends

PHMA/PPG/Acrylic copolymer = 36/36/29

Compositional analysis in the * Acrylic

PPG Acrylic
phase-separated polymer blends
*
* * Matrix
*
PHMA PHMA
20 m *
* *
Domain

Intensity (a.u.)
matrix
Inactive MDI

domain
Acrylic
Surface

PPG

PHMA

1800 1600 1400 1200 1000 800 600 400

Raman shift (cm-1)

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Applications of Raman spectroscopy

 Structural analysis of Bombyx mori silkworm

Anterior
Middle
Intensity (a. u.)

CB

Posterior

Silk gland Bombyx mori silkworm

(5th instar)

600 800 1000 1200 1400 1600 1800 2000

Posterior Middle Anterior
Silk-II (-sheet) Raman Shift (cm-1)
Isotropic Silk-I LC

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 Applications of Raman spectroscopy

 Structural analysis of PTT fibers

The most probable distribution

function based on the experimentally
determined P1 values

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Applications of Raman spectroscopy

 Structural analysis of carbon nanomaterials

1582 cm-1 : only strong band observed in
single crystalline graphite

1332 cm-1 : Diamond film

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 Applications of Raman spectroscopy

 Structural analysis of carbon nanomaterials

 G-band : In-plane vibrational mode

 D-band : the disorder-induced mode originated from the Figure. G and D band Raman spectra (top) and atomic
relatively few amorphous carbon impurities and force microscope (AFM) image (bottom) of an individual
defects in the graphene structure of the SWNTs carbon nanotube strained with an AFM tip
 Radial breathing mode (RBM) : the atomic vibration of
carbon atoms in the radial direction as if the
tube was breathing
d  248 / RBM
d : the tube diameter
wRBM : the RBM vibration frequency observed
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Applications of Raman spectroscopy

 Identification of molecular structural changes

985 cm-1: the symmetric NC

stretch (breathing mode)
of the triazine ring

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 Other Types of Raman Spectroscopy

 Resonance Raman spectroscopy

 Surface-enhanced Raman spectroscopy

(SERS)

Figure 18-13 Energy diagram for (a) resonance Raman scattering and (b)
fluorescence emission. Radiationless relaxation is shown as wavy arrows.
In the resonance Raman case, the excited electron immediately relaxes into
a vibrational level of the ground electronic state giving up a Stokes photon.
In fluorescence, relaxation to the lowest vibrational level of the excited
electronic state occurs prior to emission. Resonance Raman scattering is
 Nonlinear Raman spectroscopy nearly instantaneous, and the spectral bands are very narrow. Fluorescence
emission usually takes place on the nanosecond time scale. Fluorescence
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Other Types of Raman Spectroscopy

Quantum diagrams of the nonlinear Raman processes, with spontaneous Raman included as a reference. Levels shown are
virtual states (---) and ground and excited vibrational levels (-) in the ground electronic state of the molecule. Ground vibrational
levels are marked “G.” For each Raman process shown, arrows entering at left are incident photons, up arrows represent photon
absorption, down arrows represent photon generation, and arrows at right are output photons. Note conservation in the number
of photons created and lost in each process (each photon is represented as an arrow), l = laser frequency, s = Stokes
frequency, a = anti-Stokes frequency, v = vibrational frequency.

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