Raman: theory and instrumentation

Kit Umbach Dept. of MS&E CCMR,NBTC facilities

Outline
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1. Introduction 2. Theory
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Role of polarizability; mathematical models Depolarization ratio Temperature correction Components FT-Raman Raman microscopy

3. System instrumentation
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Light as a probe of molecular structure

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light is absorbed excitation of molecule de-excitation of molecule light is emitted visible/UV: excitation of valence electrons infrared (IR): excitation of vibrations microwave/IR: excitation of rotations

Applications
Raman Spectroscopy is a method of determining modes of molecular motions, especially vibrations. It is predominantly applicable to the qualitative and quantitative analyses of covalently bonded molecules. Characteristic regions for different groups as in IR Raman databases available Good for aqueous based samples Useful for a variety of samples, organic, inorganic & biological

Identification of phases Molecular and crystalline symmetries Identification of crystalline polymorphs Measurement of stress

History

Chandrasekhara Venkata Raman

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1888-1970 Discovered the inelastic scattering phenomenon in 1928 Was awarded the Nobel Prize for Physics in 1930

a.k.a. Sir Chandra

 Predicted in 1923, demonstrated 1928 by C.V.Raman Ramans experiment:

violet sunlight (white) Scattering liquid

violet filter

Rayleighscattered light violet green green filter green observer

Raman-scattered light

Prof. Sir C V Raman

Infrared and Raman spectroscopy are two kinds of spectroscopy a spectrum is a graph of light intensity as a function of light frequency
frequency intensity peaks in the spectrum give information about molecular structure from molecular structure, the compound can be identified

IR Spectrography - Absorption I0()

Laser Sample

I()
detector

Raman Spectrography - Scattering

Sample

0
Laser

0 - Raman 0 - Rayleigh
detector

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spectra shows vibrational frequency in wavenumbers (cm-1) peaks are used to identify chemical "groups", i.e. types of bonds examples of characteristic stretching frequencies (group frequencies) O-H N-H C-H C-O/C-N/C-C 3600 cm-1 3400 cm-1 3000 cm-1 1100-1200 cm-1 C-C 1200 cm-1 aromatic C-C 1450-1600 cm-1 C=C 1650 cm-1 CC 2200 cm-1

2150 cm

C1 C C C

1650 cm

C1 C Cl

increasing K O
1

1200 cm

C1

3000 cm

increasing ?

1200 cm

1100 cm

800 cm

Br
550 cm

 Raman based on inelastic scattering of a monochromatic excitation source - Routine energy range: 200 - 4000 cm1 - The Raman effect comprises a very small fraction, about 1 in 107 of the incident photons. Complementary selection rules to IR spectroscopy - Selection rules dictate which molecular vibrations are probed - Some vibrational modes are both IR and Raman active Great for many real-world samples - Minimal sample preparation (gas, liquid, solid) - Compatible with wet samples and normal ambient - Sample fluorescence is problematic

Polarizability in an electric field

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An electric field will distort the molecular orbital This is a weak effect that grows with the square of the intensity

Induced electric dipole moment

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An electric field can distort the electron cloud of a molecule, thereby creating an induced electric dipole moment The oscillating electric field associated with EM radiation will therefore create an oscillating induced electric dipole moment which in turn will emit, i.e. scatter, EM radiation

Raman scattering
Molecule Excitation photon hex
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Scattered photon hsc

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Rayleigh scattering: elastic interaction, no non-kinetic transfer of energy between molecule and photon, sc ex Raman scattering: inelastic interaction, transfer of energy between molecule and photon, sc ex Stokes lines: Energy of molecule increases, sc < ex Anti-stokes lines: Energy of photon increases, sc > ex

Raman selection rules

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Vibrational energy levels

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v = 1 Polarisability must change during particular vibration J = 2 Non-isotropic polarisability (ie molecule must not be spherically symmetric like CH4, SF6, etc.)

Rotational energy levels

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Combined

Vibrational Raman

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Symmetric stretching vibration of CO2 Polarisability changes

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therefore Raman band at 1,340 cm-1 no absorption at 1,340 cm-1 in IR

Dipole moment does not

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Vibrational Raman

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Asymmetric stretching vibration of CO2 Polarisability does not change during vibration
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No Raman band near 2,350 cm-1 CO2 absorbs at 2,349 cm-1 in the IR

Dipole moment does change

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Raman Spectroscopy:

Classical Treatment

Number of peaks related to degrees of freedom

DoF = 3N - 6 (bent) or 3N - 5 (linear) for N atoms

Energy related to harmonic oscillator

or =
c 2 k(m1 + m2 ) m1m2

Selection rules related to symmetry

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

CO2
Raman: 1335 cm1 IR: 2349 cm1 IR: 667 cm1

H2O
Raman + IR: 3657 cm1 Raman + IR: 3756 cm1 Raman + IR: 1594 cm1

Main Optical Transitions: Absorption, Scattering, and Fluorescence Excitation Energy, (cm1)
2nd Electronic Excited State

25,000

Impurity

1st Electronic Excited State

Elastic Scattering (Raleigh) fluorescence

fluorescence

emit

emit

emit
Electronic Ground State

4,000

Vib. states

IR

UV/Vis Fluorescence

Raman Spectroscopy: Absorption, Scattering, and Fluorescence Excitation Energy, (cm1)

2nd Electronic Excited State 25,000 1st Electronic Excited State
Stokes Anti-Stokes

emit

4,000

Vib. states

Electronic Ground State

IR

Raman
=emit

Resonance Raman
=emit

Raman Spectroscopy: Absorption, Scattering, and Fluorescence Excitation Energy, (cm1)

2nd Electronic Excited State

25,000

Impurity

1st Electronic Excited State

Stokes

Anti-Stokes fluorescence

4,000

fluorescence

emit

Vib. states

Electronic Ground State

IR

Raman
=emit-

Fluorescence = Trouble

Raman Spectrum
A Raman spectrum is a plot of the intensity of Raman scattered radiation as a function of its frequency difference from the incident radiation (usually in units of wavenumbers, cm-1). This difference is called the Raman shift. At the very most, the intensities of Raman lines are 0.001 % of the intensity of the source; as a consequence, their detection and measurement are somewhat more difficult than are infrared spectra

Raman Spectrum of CCl4

The intensity or power of a normal Raman peak depends in a complex way upon the polarizability of the molecule, the intensity of the source, and the concentration of the active group. 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.

Stokes and anti-Stokes

As you can see, the Stokes peaks correspond to lower photon frequencies and lower energies. The antiStokes side is symmetric but corresponds to higher frequencies and energies. The Stokes lines are stronger because the population of molecules at =0 is much larger than at =1 by the MaxwellBoltzmann distribution law.

Advantages of Raman
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Selection rules allow for some vibrations (normally symmetric) to be seen only by Raman spectroscopy. Measurements of depolarization ratios yield information about molecular symmetry. Only a small sample area is needed (laser spot). Water is a weak Raman scatterer, allowing for the use of aqueous solutions. Can also sample through glass container walls. The region 4000 cm-1 to 50 cm-1 can be covered in a single scan without changing gratings, splitters, detectors, etc.

The simplest real vibrating system: a diatomic molecule

x1 m1 K m2 x2

m1m 2 d 2 x1 d 2 x 2 dt 2 + dt 2 = K (x1 + x 2 ) m1 + m 2
Reduced mass

d 2q 2 = K q dt

displacement

Just like Hookes law: F=kX

q = q 0 cos(2 m t )
Where:

m =

1 K 2

Scattering of radiation from a diatomic molecule

q = q 0 cos(2 m t ) E = E 0 cos(20 t )
?

Induced dipole moment:

P = E = E 0 cos(20 t )

For a small amplitude of vibration, the polarizability is a linear function of q:

= 0 + q + K q q = 0

P = 0 E 0 cos(20 t ) + q 0 cos(2m t ) E 0 cos(20 t ) = q q = 0 1 = 0 E 0 cos(20 t ) + q 0 E 0 [cos(2{ 0 m } t )+ cos(2{ 0 + m } t )] q 2 q = 0

Rayleigh scattering Stokes scattering Anti-Stokes scattering

Selection rules for vibrations

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IR absorption: electric dipole moment of molecule changes during vibration o electric dipole moment is net separation of + and charge tends to show peaks for polar bonds and non-symmetric vibrations o NO for H2 stretch and CO2 symmetric stretch o YES for CO2 asymmetric stretch and bend

Raman scattering: polarisability of molecule changes during vibration o polarisability is related to how easily a molecule can be deformed tends to show peaks for homopolar bonds and symmetric vibrations o NO for CO2 asymmetric stretch and bend o YES for H2 stretch and CO2 symmetric stretch

More math
In actual molecules, the nice linear relationship does not hold since both P and E are vectors. Then the equation must be written as Px xx xy xzEx Py = yx yy yzEy Pz zx zy zz Ez
The matrix is called the polarizability tensor. We can plot i ( in the i

direction) in all directions we get a 3D surface. Conventionally we plot 1/ i instead, and get a polarizability ellipsoid.

Selection rules
0 and 1 are the wavefunctions of a molecule before and after a vibrational transition, respectively.

Ii = 0 i 1 dV 0 x i 1 dV
i ( i = x,y,z ) are the components of the dipole moment. If one of the integrals i 0, than the transition is IR active
Px xx P = y yx Pz zx xz E x yz E y zz E z

xy yy zy

Iij = 0 ij 1 dV 0 x i x j 1 dV
ij ( i,j = x,y,z ) are the components of the polarizability tensor. If one of the integrals ij 0, than the transition is Raman active

CO2 Polarizability ellipsoids

Raman active

IR active

IR active

Modes of H2O

All the modes are both Raman & IR Active

The simplest Raman active crystal: 1D chain with 2 atoms in the unit cell
m1 u2n Equations of motion: K m2 u2n+1

m1&& 2 n = K (u 2 n +1 + u 2 n 1 2u 2 n ) u m 2&& 2 n = K (u 2 n + 2 + u 2 n 2u 2 n +1 ) u

Assume the solutions:

u 2 n = A1 exp i[2t + 2nka ] u 2 n +1 = A 2 exp i[2t + (2n + 1)ka ]

1 K K 2 4K 2 sin 2 ka Obtain the frequencies: = 2 2 m1m 2 4

2

The phonon spectrum

IR & Raman Active

Scattering
the observed intensity of Raman scattering is proportional to IR = (0j)4j2Qj2 where 0 is the laser light frequency, j is the frequency of the jth mode, Qj the displacement, and is the polarizability of that mode. Note the dependence on the fourth power of the laser light, typical for dipole scattering.
oClassically,

Polarization
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Incident laser light is plane-polarized Scattered light may become de- polarized

Depolarization occurs for the less symmetrical vibrational modes

Depolarization
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Put a (plane) polarizing filter between sample and detector Acquire spectrum with polarizing filter parallel to laser plane polarization

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Rotate polarizing filter 90, reacquire spectrum Compare relative intensities of bands in the two spectra

Depolarization
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Define depolarization ratio

I = I ||
0 < < 0.75, band is said to be polarized = 0.75, band is said to be depolarized

Polarization
Raman: - totally symmetric vibrations produce polarized bands, 0 < < 0.75
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- non-totally symmetric vibrations produce depolarized bands, = 0.75 - polarization measurements can help identify (symmetry) type of vibration producing a band

Depolarization ratio
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The depolarization ratio is defined as the ratio of the light scattered at 90 degrees that is perpendicular (Iy) to the light that is parallel (I||) with respect to the incident light. The incident laser light is already polarized. But the scrambler is required because monochromator gratings show different efficiencies for the different polarizations.

Ez Iz (I|| ) Analyzer Iy (I ) Scrambler Incident laser beam y

x Direction of observation

(Original diagram from J.R. Ferraro, in References)

Depolarization ratio
Since the ratio is defined as p = polarizability matrix by

Iy , and it can be shown that this is related to the Iz

2 1 xx + yy + zz ) ( 3 1 g s = [( xx yy ) 2 + ( yy zz ) 2 + ( zz xx ) 2 ] 3 1 + [( xy + yx ) 2 + ( yz + zy ) 2 + ( xz + zx ) 2 ] 2 1 g a = [( xy yx ) 2 + ( xz zx ) 2 + ( yz zy ) 2 ] 2

3g s + 5g a p = , 0 s 10g + 4g

g0 =

where

In normal Raman scattering, ga = 0 from symmetry. For totally symmetric vibration, we 3 3 then get 0 p < , while for non-totally symmetric vibration p = 4 4

Depolarization of CCl4
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In the spectrum on the left you see the totally symmetric vibrations of CCl4 (459 cm-1) and the non-totally symmetric modes (314 and 218 cm-1), taken in a 90 scattering geometry. The values of p were 0.02 for the first case (459 cm-1; note ratio of peaks), and 0.75 for the other two peaks, as expected. Though usually done with liquids and gases, depolarization measurements can be done in solids by suspending them in a material with a similar index.

Examples: CCl4
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CCl4 has 9 vibrational modes:

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anti-symmetric stretch (3 degeneracy) symmetric stretch anti-sym. bend (3 degeneracy) sym. bend or twist (2 degeneracy)

458 cm-1

790 cm-1

frequency of vibration: asym. bend () > twist ()

314 cm-1

218 cm-1

CCl4 modes and Raman

oAnimation

from

http://fy.chalmers.se/~b rodin/MolecularMotions/ CCl4molecule.html

Temperature correction
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The thermal population factor can mask peaks or bands in the low-frequency region of the spectrum. The corrected (reduced) Raman intensity can be calculated from
Ireduced Iobserved = h Exp + 1 kT

This needs to be done before any peak assignments are made

Temperature correction
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The effect of the temperature correction can be seen at left, where the most dramatic change occurs at low wavenumbers.

Modern Raman Spectrometers

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FT-Raman spectrometers also make use of Michelson interferometers o Use IR (1 m) lasers, almost no problem with fluorescence for organic molecules o Have many of the same advantages of FT-IR over dispersive o But, there is much debate about the role of shot noise and whether signal averaging is really effective CCD-Raman spectrometers dispersive spectrometers that use a CCD detector o Raman is detected at optical frequencies! o Generally more sensitive, used for microscopy o Usually more susceptible to fluorescence, also more complex Detectors - GaAs photomultiplier tubes, diode arrays, in addition to the above.

Dispersive and FTRaman Spectrometry

McCreery, R. L., Raman McCreery, Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New ed., York: 2000

Sample Illumination System

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Liquid Samples: A major advantage of sample handling in Raman spectroscopy compared with infrared arises because water is a weak Raman scatterer but a strong absorber of infrared radiation. Thus, aqueous solutions can be studied by Raman spectroscopy but not by infrared. This advantage is particularly important for biological and inorganic systems and in studies dealing with water pollution problems. Solid Samples: Raman spectra of solid samples are often acquired by filling a small cavity with the sample after it has been ground to a fine powder. Polymers can usually be examined directly with no sample pretreatment.

Simplified Raman spectrometer layout

Lasers
For a long time the most common laser for a Raman system was the Ar:ion laser, which provided multiple lines (wavelengths). Cost was significant, however, as were maintenance costs. Nowadays the selection is much greater: Gas Ion, HeNe, DPSS 532 nm, Solid-state visible lasers, NIR Diode, High power fibre linked, UV lasers The key is what laser can minimize the fluorescence signal of the sample. On the left we see a sample irradiated with green light (too fluorescent); red light (still too much), and NIR (785 nm; just right)

A Typical Raman System

Typical geometries for Raman scattering

90o scattering

180o scattering

Spectrographs
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The most common spetrograph arrangement is the Czerny-Turner, shown on the right. The mirrors are used as collimators, and the turret contains planar reflective gratings.

Spectrographs
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For higher resolution and rejection of unwanted (read Rayleigh) wavelengths, one can use a double or triple monochromator. This adds to the price and diminishes the overall light signal.

CCD Detectors
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Most of the current dispersive Raman set-ups are now equipped with multichannel twodimensional CCD detectors. The main advantages of these detectors are the high quantum efficiency, the extremely low level of thermal noise (when effectively cooled), low read noise and the large spectral range available. Many CCD chips exist, but one of the most common spectroscopy sensor formats is the 1024 x 256 pixel array.

FT-Raman

Advantages and disadvantages of FT-Raman

Use of NIR lasers greatly reduces fluorescence problem o Relatively inexpensive o High resolution, high throughput o Collects Stokes and Anti-Stokes simultaneously o Can be attached to an IR instrument But o Black body emissions at higher temp swamp Raman o Lower scattering intensity due to use of NIR (4 effect) o Absorptions in the NIR o Slow (tens of minutes in some systems)
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Michelson interferometer

3D view
FTIR

FT-Raman schematic

Inteferometers

For monochromatic radiation, the interferogram looks like a cosine curve For polychromatic radiation, each frequency is encoded with a much slower amplitude modulation The relationship between frequencies:
f = 2v M c

Where: is the frequency of the radiation c is the speed of light in cm/s vm is the mirror velocity in cm/s

Example: mirror rate = 0.3 cm/s modulates 1000 cm-1 light at 600 Hz Example: mirror rate = 0.2 cm/s modulates 700 nm light at 5700 Hz

Raman microscopes

Microscope schematic

Conventional vs. Confocal