Raman Spectroscopy: Introductory Tutorial

Daniel T. Schwartz
Department of Chemical Engineering
Box 351750
University of Washington
Seattle, WA 98195-1750
[email protected]

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

Raman Spectroscopy: General

• Group assignments identify characteristic vibrational energy

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

c k(m1 + m 2 )
σ or Δσ =
2π m1m 2
• Selection rules related to symmetry
Rule of thumb: symmetric=Raman active, asymmetric=IR active
€

CO2 H2O
Raman: 1335 cm–1
Raman + IR: 3657 cm–1
IR: 2349 cm–1
Raman + IR: 3756 cm–1

IR: 667 cm–1

Raman + IR: 1594 cm–1
Main Optical Transitions: Absorption, Scattering, and Fluorescence

2nd Electronic
Excited State
Excitation Energy,  (cm–1)

Impurity
25,000

1st Electronic
Excited State
Elastic
Scattering
(Raleigh)

fluorescence
 emit
 emit

fluorescence
emit

4,000 Vib.
 states Electronic
Ground State
0
IR UV/Vis
Fluorescence
Raman Spectroscopy: Absorption, Scattering, and Fluorescence

2nd Electronic
Excited State
Excitation Energy,  (cm–1)

25,000

1st Electronic
Excited State
Stokes Anti-Stokes

 emit

4,000 Vib.
 ±∆ states ∆ Electronic
Ground State
0
IR Raman Resonance Raman
 ∆=emit– ∆=emit–
Raman Spectroscopy: At NTUF, you pick the Laser Excitation
Near IR Visible
785 nm 514 nm
Intensity

Stokes Anti-Stokes
Stokes Anti-Stokes

–∆ +∆ –∆ +∆

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

Excitation Energy,  (cm–1)

Raman Spectroscopy: Absorption, Scattering, and Fluorescence

2nd Electronic
Excited State
Excitation Energy,  (cm–1)

Impurity
25,000

1st Electronic
Excited State
Stokes Anti-Stokes

fluorescence
 emit

4,000 fluorescence Vib.

 ∆ states Electronic
Ground State
0
IR Raman Fluorescence
 ∆=emit- = Trouble
Raman Spectroscopy: Coping w/ Fluorescence

1. Use NTUF 785 nm laser line (excites many fewer fluorophores)

2. Photobleach with long exposure laser irradiation.

Poly (diallyl phthalate)

ex = 514.5 nm
Raman Intensity

Without Bleaching

After 2 hours Bleaching

1000 2000 3000

Raman Shift (cm-1)
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 preparation…gas, 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: Dan’s 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: Dan’s trip to NTUF

Flow Field Plate - Graphite

⎛ Ig ⎞
⎜ ⎟ = 3.98
⎝ Id ⎠ Nanocrystalline graphite has graphitic (g)
and disorder (d) peaks. The characteristic
dimension of graphitic domains is given by:
€
⎛ Ig ⎞
l(Å) = 44 ⎜ ⎟
⎝Id ⎠
= 175Å

From early literature on graphitic materials

Tuinstra and Koenig, J. Chem Phys. 53, 1126 (1970).
Raman Spectroscopy: Dan’s trip to NTUF

Gas Diffusion Layers

(graphite paper)

l(Å) = 161Å

l(Å) = 76 Å

€
Raman Spectroscopy: Dan’s trip to NTUF

Gas Diffusion Layers

(Woven Fibers)

l(Å) = 55 Å

€
Raman Spectroscopy: Dan’s trip to NTUF

Nafion

Fluorescence problems!
Maybe try photobleaching
as next option.