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Instrumental Analysis

Choi, Hyun Chul

Department of Chemistry
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Raman Spectroscopy
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Solar radiation spectrum
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Raman spectroscopy: some sources

General Principles and Instrumentation:

Principles of Instrumental Analysis, by Douglas A. Skoog, F. James Holler,
Timothy A. Nieman

Inorganic:
Infrared and Raman Spectra of Inorganic and Coordination Compounds :
Theory and Applications in Inorganic Chemistry (Volume A) by Kazuo
Nakamoto

Infrared and Raman Spectra of Inorganic and Coordination Compounds :

Applications in Coordination, Organometallic, and Bioinorganic Chemistry
(Volume B) by Kazuo Nakamoto

Organic:
The Handbook of Infrared and Raman Characteristic Frequencies of Organic
Molecules by Daimay Lin-Vien, et al
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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 – Lower cost 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…
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Why collect Raman spectra?

 Chemical and Structural Information

 Qualitative and Quantitative
 Rapid and Sensitive (only micron-sized particles needed)
 Microgram or Bulk Samples
 Non-contact and Non-destructive
 QC or R & D
 Simple Sampling Conditions
 Sample container often unimportant (bags, bottles)
 Complementary to FT-IR Data
 Often succeeds where IR cannot
 Raman and photoluminescence data collected simultaneously
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Raman spectroscopy: overview

• A vibrational spectroscopy
- IR and Raman are the most common vibrational spectroscopies for
assessing molecular motion and fingerprinting species
- Based on inelastic scattering of a monochromatic excitation source
- Routine energy range: 200 - 4000 cm–1

absorption

A molecule can be characterized

(and identified) based on the
position and intensity of the
spectral peaks by either FT/IR or
Scattering (emission) Raman spectroscopy
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IR vs. Raman spetrometer
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Energy levels in infrared absorption

Excited states

h

Infrared Absorption and Emission

h(2 - 1) (overtone)

3
2 h(1 - 0 ) h(1 - 0)
Ground
1 (vibrational)
0 states

Infrared absorption occurs among the ground vibrational states, the

energy differences, and corresponding spectrum, determined by the
specific molecular vibration(s). The infrared absorption is a net energy
gain for the molecule and recorded as an energy loss for the analysis
beam.
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Energy levels in Raman scattering

excited states

h x
Rayleigh Stokes anti-Stokes
virtual states
h0 h0 h(0 - 1) h(0 + 1 )

3 ground

12 (vibrational) states
0

Rayleigh scattered light undergoes no energy change and corresponds to the laser
wavelength. Stokes scattering, the 'normal' Raman peaks, are at lower energy
relative to the laser (red shift) while anti-Stokes scattering (usually much weaker) is
at higher energy than the laser wavelength.
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Raman scattering

When a sample is irradiated with monochromatic light

(e. g. with laser light using discrete lines between 300 and 1064 nm)

Different physical phenomena happen:

1. The main part of the incident light is transmitted without interaction

2. Roughly 10-4 part of the light is elastically scattered

with no energy absorption --->Rayleigh line

3. A part of the incident light may be absorbed by electronic transitions

and is emitted as ---> Flourescence

4. Only 10-8 of the incident light is inelastically scattered and interacts

with the sample .
The energy is partly absorbed ---> Raman spectrum
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Raman spectrum

,The Raman effect comprises a very small fraction

.about 1 in 107 of the incident photons
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Raman scattering : classical treatment

From the dielectric function

-Of a collection of simple harmonic oscillators with density N,
charge Q, Mass M and natural frequencies ωi is:
4 NQ 2
  1 
i M (  i )

In a dielectric medium the electric force is different from the

one in vacuum due to polarizability:
Pi (k ,  )  ij ( ) E j (k ,  )  
 ij  1  4 ij E P

Radiation of an oscillating dipole P

dI 2 2 2
  4 P  es sin 2 ( ) I   P  e s   ei  ij ( ) E j (k ,  )e s
4 4
d
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• Atomic thermal vibrations (or any other density fluctuations)

denoted (r,t) can be expanded as plane waves:

ρ(r, t )   Q(q,  )ei (qr t )

q

• The electric susceptibilty is fluctuating due to these thermal

vibrations and can be expanded from zero temperature value
(treating separately each normal mode) as


 (i , Q)   0 (i )   Q(q, 0 )ei ( qr 0t )
Q 0
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• Since P   E the polarizability also fluctuate

P(k i , i )  P0  Pind    0 (i )   ind (i , Q)  E(k i , i )



Pind (r , t , Q)   Q(q, 0 ) Re ei (qr 0t ) E( ki , i ) Re ei ( k i r it )
Q 0

1 
 Q(q, 0 )E(ki , i ) 
2 Q 0
i ( k i q )r  (i 0 ) t  i  ( k i q )r  (i 0 ) t 
Re(e  e  )
anti Stokes Stokes

Pind is an oscillating dipole and therefore it radiates.

This radiation is Raman Scattering.
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Example : simple diatomic system

x1 K x2

m1 m2

m1m 2  d 2 x1 d 2 x 2  Just like

  2    K  x1  x 2 
m1  m 2  dt 2
dt  Hooke’s law:
F=kX
Reduced displacement
d 2q
mass  2  K  q
dt

 q  q 0 cos 2 m  t 

1 K
:Where m 
2 
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q  q 0 cos 2 m  t 

E  E 0 cos 20  t  ?

Induced dipole moment: P   E   E 0 cos 20  t 

For a small amplitude of vibration, the   

polarizability a is a linear function of    0     q  
q:
 q q  0

  
 P   0 E 0 cos 20  t      q 0 cos 2m  t   E 0 cos 20  t  
 q q  0
1   
  0 E 0 cos 20  t     q 0 E 0  cos 2  0   m   t   cos 2  0   m   t  
2  q q  0

Rayleigh Stokes Anti-Stokes

scattering scattering scattering
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Raman scattering : 1D chain with 2 atoms

x1 K x2

m1 m2

Equations of m1u 2 n  K  u 2 n 1  u 2 n 1  2u 2 n 
:motion m 2u 2 n  K  u 2 n  2  u 2 n  2u 2 n 1 

Assume the u 2 n  A1  exp i 2t  2nka 

:solutions u 2 n 1  A 2  exp i 2t   2n  1 ka 

2 1 K K 2 4K 2 sin 2 ka 
Obtain the   2  2
 
:frequencies 4    m1m 2 

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Raman scattering : quantum treatment

Oscillating dipole doesn’t radiate. Quantum transitions do.

- transition probabilities are calculated with fermi golden rule
2 2
w g( s , E f ) f H i  ( i   s  Ei  E f )

with H  H crystal  H Rad  H int
H int  H eR  H ph  R

H crystal  H e  H ph  H e  ph

• phonon-photon interaction is weak, since

• semi classical approach – ignore Hrad
• HeR is treated in the electric dipole approximation.
• adiabatic approximation. Electrons are in the ground state before and after

the scattering
•The state of the crystal is separated to a product of electrons state and
phonon states.
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Incoming Photon interacts with an electron. the Photon is annihilated and the electron is
excited to an intermediate virtual state |b>. The excited electron interact with a phonon,
and returns to the electronic ground state creating a scattered Photon.

2 2
w g( s , E f ) f H i  ( i   s  Ei  E f )

 g , Q f H eR  a , Q f  a , Q f H eL  b , Qi  b , Qi H eR  g , Qi
f H i  
a ,b (i  Eb )(s  Ea )
 g , Q f H eL  a , Qi  a , Qi H eR  b , Qi  b , Qi H eR  g , Qi
a ,b (i  Eb )(0  Ea )

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Selection rule

y0 and y1 are the wavefunctions of a ‘molecule’ before and after a

vibrational transition, respectively.
Ii    0 i 1 dV    0 x i 1 dV

mi ( i = x,y,z ) are the components of the dipole moment.

If one of the integrals Ii  0, than the transition is IR active

Px   xx  xy  xz  E x 
 P     yy

 yz  E y 
 y   yx  
 Pz    zx  zy  zz   E z 

Iij    0 ij 1 dV    0 x i x j 1 dV

aij ( i,j = x,y,z ) are the components of the polarizability tensor.

If one of the integrals Iij  0, than the transition is Raman active
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Summary

• Number of peaks related to degrees of freedom

DoF = 3N - 6 (bent) or 3N - 5 (linear) for N atoms
• Energy related to harmonic oscillator
c k(m1  m 2 )
 or  
2 m1m 2

• Selection rules related to symmetry

Rule of thumb: symmetric = Raman active, asymmetric = IR active

• Raman intensity
IR = N I 0 K  4  2
N ; number of molecules, I0 ; Incident laser intensity K ; Instrumental
function,  ; Excitation frequency ; Polarizability tensor
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Problems : laser source effect
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Problems : fluorescence
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Poly (diallyl phthalate)

ex = 514.5 nm
Raman Intensity

Without Bleaching

After 2 hours Bleaching

1000 2000 3000

Raman Shift (cm-1)
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Raman modes

Dispersive (a.k.a. spontaneous)

Fourier-transform
Surface enhanced (SERS)
Coherent anti-Stokes (CARS)
Resonance Raman
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Module Normal Raman Resonance Raman Time-Resolved FT-Raman

Laser cw laser Pulse laser Synchronous- Nd-YAG
Source Ar+: Nd-YAG (1064)- pumped (1064nm)
488, 514.5 Excimer(XeCl,308)- dye laser
+
Kr : pumped dye laser
531, 647.1 cw laser
He-Ne : 632.8 Ar+ or Kr+ based

 Double, Single Single, Double, Triple Single, Double, Interferometer

Isolation monochromator monochromator Triple
monochromat
or
Detector PMT PMT PMT Ge, 77K
PDA PDA PDA InGaAs, 77K
CCD CCD CCD
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Applications

2.0 1.5
RAMANINTENSITY
1.0 0.5
0.0
4 50 400 350 3 00 250 200 15 0 1 00
WAVENUMBERCM-1

Red ink: Cinnabar (HgS)

Piece of medieval manuscript

Surface map by FT-Raman

spectroscopy
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With courtesy of Prof. Ernst, ETH Zürich

Ancient tibetian Mandala

0.1 0
0.0 20
18
0.0 80.0 6 0.0 16
Ra man In ten sity
0.0 14
0.012
0.0 4
0.0 080.0 20.0 10
060
0.0
0.0

1000
800 9 00 700 800 600 700 500
6 00 5004 00 4 00 300 300 200
200 100
Waven umber cm- 1

1(rot),
O:\3OG_Ettlingen\CL\Spektren\Prof Ernst\FRA\Grosses Bild 1, 4 FRA
(gelb), Sonde.1
FRA Sonde.1 Grosses Bild
Grosses 1, 1,
Bild 1(rot), FRAFRA
4 (gelb), Sonde
Sonde E55+FRA106/S; FT-Raman
E55+FRA106/S; FT-Raman
10/09/2002

Blue:
Red: Spectrum of red
yellow
areaarea
in Mandala
in Mandala Ernst\RFS\1, weisser Untergrund, Sonde.1
O:\3OG_Ettlingen\CL\Spektren\Prof Ernst\RFS\6, Sonde.5 1, weisser Untergrund, Sonde
6, FT-Raman, RFS100/S 2002/08/14

Black: ReferenceSpectrum
Blue: Reference spectrum of of Cinnabar
Auripigment