Raman Spectroscopy: Introductory Tutorial

Daniel T. Schwartz

Department of Chemical Engineering
Box 351750
University of Washington
Seattle, WA 98195-1750

dts@u.washington.edu
Goal of the tutorial is to answer the questions,

What is Raman spectroscopy and can the new
Raman microscope at NTUF help with my sample?
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
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


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
- Achilles Heal is sample fluorescence
Raman Spectroscopy: General
IR and Raman are both useful for Fingerprinting

















Symmetry dictates which are active in Raman and IR
Group assignments identify characteristic vibrational energy
Raman Spectroscopy: General
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

Selection rules related to symmetry
Rule of thumb: symmetric=Raman active, asymmetric=IR active
Raman: 1335 cm
1

IR: 2349 cm
1

IR: 667 cm
1

CO
2


o or Ao =
c
2t
k(m
1
+m
2
)
m
1
m
2
Raman + IR: 3657 cm
1

Raman + IR: 3756 cm
1

Raman + IR: 1594 cm
1

H
2
O
Electronic
Ground State
1st Electronic
Excited State
E
x
c
i
t
a
t
i
o
n

E
n
e
r
g
y
,

o

(
c
m

1
)

Vib.
states
4,000
25,000
0
IR
2nd Electronic
Excited State
o
o o
emit

f
l
u
o
r
e
s
c
e
n
c
e

I
m
p
u
r
i
t
y

o
emit

f
l
u
o
r
e
s
c
e
n
c
e

UV/Vis
Fluorescence
o
emit
o
Elastic
Scattering
(Raleigh)
Main Optical Transitions: Absorption, Scattering, and Fluorescence
Electronic
Ground State
1st Electronic
Excited State
E
x
c
i
t
a
t
i
o
n

E
n
e
r
g
y
,

o

(
c
m

1
)

Vib.
states
4,000
25,000
0
IR
o
o o
emit

2nd Electronic
Excited State
Raman
o=o
emit
o
o o o
Resonance Raman
o=o
emit
o
Raman Spectroscopy: Absorption, Scattering, and Fluorescence
Stokes Anti-Stokes
Excitation Energy, o (cm
1
)
Raman Spectroscopy: At NTUF, you pick the Laser Excitation
I
n
t
e
n
s
i
t
y

11,000 13,000 15,000 17,000 19,000 21,000

Near IR
785 nm

Visible
514 nm
o +o o +o
Stokes Anti-Stokes
Stokes Anti-Stokes
Electronic
Ground State
1st Electronic
Excited State
E
x
c
i
t
a
t
i
o
n

E
n
e
r
g
y
,

o

(
c
m

1
)

Vib.
states
4,000
25,000
0
f
l
u
o
r
e
s
c
e
n
c
e

IR
o
o o
emit

2nd Electronic
Excited State
Raman
o=o
emit
-o
o o
f
l
u
o
r
e
s
c
e
n
c
e

I
m
p
u
r
i
t
y

Fluorescence
= Trouble
Raman Spectroscopy: Absorption, Scattering, and Fluorescence
Stokes Anti-Stokes
1000 2000 3000
Raman Shift (cm
-1
)
R
a
m
a
n

I
n
t
e
n
s
i
t
y


Without Bleaching
After 2 hours Bleaching
Poly (diallyl phthalate)

ex
= 514.5 nm
Raman Spectroscopy: Coping w/ Fluorescence
1. Use NTUF 785 nm laser line (excites many fewer fluorophores)

2. Photobleach with long exposure laser irradiation.
Raman Spectroscopy: Summary
1. Raman is a vibrational spectroscopy akin to IR
- Good for fingerprinting, probing molecular symmetry

2. Scattering-based, not transmission/reflection
- Means no need for fancy sample preparationgas, liquid, or solid
- Virtually always use anti-Stokes lines due to stronger signal

3. You need to pick excitation energy (laser line)
- 785 nm: Fluorescence less probable; Lower Raman signal
- 514 nm: Fluorescence more probable; Resonance more likely; Higher signal

4. Other things not talked about
- SERS: Surface Enhanced Raman Spectroscopy
- Quantum origins of selection rules and scattering cross-section
Raman Spectroscopy: Dans trip to NTUF
Fuel Cell Materials --- picked because I had little Raman experience
with these materials
From http://www.fueleconomy.gov/feg/fc_pics/fuel_cell_still.gif
Raman Spectroscopy: Dans trip to NTUF
Flow Field Plate - Graphite
From early literature on graphitic materials
Tuinstra and Koenig, J. Chem Phys. 53, 1126 (1970).

() = 44
I
g
I
d
|
\

|
.
|
= 175

I
g
I
d
|
\

|
.
|
= 3.98
Nanocrystalline graphite has graphitic (g)
and disorder (d) peaks. The characteristic
dimension of graphitic domains is given by:
Raman Spectroscopy: Dans trip to NTUF
Gas Diffusion Layers
(graphite paper)

() = 76

() = 161
Raman Spectroscopy: Dans trip to NTUF
Gas Diffusion Layers
(Woven Fibers)

() = 55
Raman Spectroscopy: Dans trip to NTUF
Nafion

Fluorescence problems!
Maybe try photobleaching
as next option.