Introduction to Infrared

Spectroscopy
 Infrared (IR) Region

12500 ～ 4000 cm-1 4000 ～ 667 cm-1 667 ～ 10 cm-1

Near infrared Mid Infrared Far Infrared
（780 nm ～ 2.5 µm） （2.5 µm ～ 15 µm） （15 µm ～ 2000 µm）
 100% transmission
 Peak absorptions are shown
as the region facing downwards
 Vibrational / Rotational
No. Region Range cm -1 Information

1 Near IR 12500 - 4000 Changes in Vibrational and

rotational levels, electron transitions

2 Mid-IR 4000 - 667 Changes in fundamental Vibrational

levels of most molecules

3 Far-IR 667 - 10 Rotational energy level changes

 Terms and Definitions
• Spectroscopy - the study of interaction of light
with matter
• Infrared spectroscopy - the study of
interaction of infrared light with matter
• Mid-Infrared - light from 4000-400cm-1
• Spectrometer - An instrument that measures a
spectrum
• Spectrum – a plot of measured light intensity
vs. some property of light (wavelength &
wavenumber)
 The Properties of Light

Light is a type of electromagnetic radiation.

The wave properties of electromagnetic radiation are

described by three variables:
• frequency (), cycles per second
• wavelength (), the distance a wave travels in one
cycle
• amplitude, the height of a wave crest or depth of a
trough. E ∝ A2
The reciprocal relationship of frequency and wavelength
Differing amplitude (brightness, or intensity) of a wave
Different behaviors of waves
Formation of a diffraction pattern.
 Energy and Frequency
Color is related to wavelength and frequency, while
temperature is related to energy.

Energy is therefore related to frequency and wavelength:

E = hc E = light energy in Joules

c is speed of light in a vacuum, 3.00 x 108 m/s
h is Planck’s constant

Wavenumber, W = cycles/distance (1/)

E = hcW
c = v
c = v/W
 What Is An Infrared Spectrum?
• A plot of measured infrared light intensity vs a property
of light
• The y-axis can be plotted in absorbance/%transmittance
units
• The x-axis is plotted in wavenumbers
 In Absorbance units (quantitative)
A = log(I0/I)
A = absorbance (amount of absorption)
I0 = Intensity in the background spectrum
I = Intensity in the sample spectrum

A is related to concentration of molecules in a sample

via Beer’s Law,
A = Ɛlc Peak height(peak area) ∝ concentration
A = absorbance
Ɛ = absorptivity, absolute measurement of IR absorbance at a
specific W
l = pathlength (sample thickness)
c = concentration
When measuring IR spectra, peaks should be less than 2
absorbance units or greater than 10% transmittance to avoid
truncated peaks
 In % T (qualitative)
A = log 1/T
%T = 100 x (I/I0)
%T = Percent transmittance
I0 = Intensity in the background spectrum
I = Intensity in the sample spectrum
%T spectra are NOT linearly proportional to c,
used for qualitative analysis only
A and %T are mathematically related, can be
interconverted using FTIR software
 What Are IR Spectra used for?
1. Unknown analysis (what molecules are present in a sample?)
How? Peak positions in IR spectra correlate with molecular
structure
2. Sample Identification (are two samples the same?)
How? Compare unknown spectra with sample spectra by noting
how well the peak positions, heights and widths in these spectra
match
3. Determination of sample concentration
How? (i) Measure spectra of samples of known concentrations
(standards). These concentrations must bracket the expected
concentration range of compounds in unknowns. (ii) Prepare a
calibration curve relating A and c using Beer’s Law
 Advantages and Disadvantages of IR Spectroscopy

Advantages Disadvantages

• Almost universal • Can’t detect some

molecules (monatomic ions,
• Spectra are information rich
noble gases not chemically
• Relatively fast and easy bonded to anything)
• Relatively inexpensive • Mixtures
• High sensitivity • Water
 Advantages and Disadvantages of FTIR Spectroscopy
Advantages Disadvantages
• Throughput advantage (Jacquinot • Artifacts (peaks
advantage) from water vapor
• Combining multiple signals (from and CO2)
multiple wavemenghts) into one • Instrument
(Multiplex/Fellgett’s advantage) that response function
leads to improved SNR (limits accuracy of
• Wavenumber precision (± 0.01cm-1) spectroscopic
-measure of reproducibility parameters by
• Internally calibrated (HeNe broadening
reference laser as an internal recorded spectral
wavelength calibration standard lines/features
(Connes advantage)
 Comparison of FTIR & IR Spectroscopy
Dispersive IR Fourier transform IR
1. There are many moving parts, resulting 1. Only the mirror moves during the
in mechanical slippage. experiment.

2. Calibration against reference spectra is 2. Use of laser provides high frequency

required to measure frequency. accuracy (to 0.01 cm-1).

3. Stray light causes spurious readings. 3. Stray radiations do not affect the
detector.

4. To improve resolution only a small 4. A much larger beam may be used at all
amount of IR beam is allowed to pass. time. Data collection is easier.

5. Only radiation of a narrow frequency 5. All frequency of radiation falls on the

range falls on the detector at one time. detector simultaneously.

6. Slow scan speed. 6. Rapid scan speed

How an FTIR Works?
How light interference and an interferogram produce a
spectrum?
Light interference:
• the phenomena of multiple light waves interfering
with one another under certain circumstances,
• constructive vs destructive

An interferogram:
• a plot of light intensity vs OPD
• a fundamental measurement obtained by FTIR
spectrophotometer
• A superposition of sine and cosine waves
• electrical signals coming out of detector
Interferometers and Interferograms

• Light enters interferometer is split into two beams

• Light beams travel two different paths, D1, D2
• Optical path difference (OPD), ẟ = D2-D1
• When ẟ = 0, known as ZPD
Michelson interferometer
Af = A 1 + A 2

Af = final amplitude
A1 = amplitude of fixed mirror
A2 = amplitude of mobile mirror Aligns a beam of waves in a
specific direction
 Phase of a wave
• A measure of how far through the cycle a
wave is at a particular point in space and time
OR
• Position of a point within a wave cycle
For constructive interferences: ẟ = nλ, n = 0, 1, 2….(an integer)
--> Af > A1 or A2

At ZPD,
ẟ=0

n=1
Phase difference = λ
Moving the mirror in a small
distance affects light intensity of
exiting beam

When ẟ ≠ 0; ẟ = 2∆
∆ = mirror displacement

For destructive interferences:

ẟ = (n + 1/2)λ, n = 0, 1, 2…(an interger) --> Af < A1 or A2

n = 1/2

Phase difference ½ λ
• Interferogram of a single • Interferograms of λ light, 3λ
wavelength of light (laser) light and their sum
passing through the
interferometer
Frequency of light (IR source) vs frequency of electrical
signal (Fourier frequency in interferogram)

F = (2Vv)/c
F = Fourier frequency of interferogram in Hz
V = frequency of light wave in Hz
v = velocity of moving mirror in cm/s
c = speed of light in cm/s

F = 2vW
F = Fourier frequency of interferogram in Hz
v = velocity of moving mirror in cm/s
W = wavenumber in cm-1
• An IR spectrum consists of two important info: light
intensity and wavenumber.
• Fourier frequencies (F) in an interferogram tell us
what wavenumber of light are present in a given light
beam
• Amplitude of F ∝ amount of light reaches detector at
that wavelength
• When light of all wavenumbers from IR source passes
through interferometer, each wavelength exists an
interferogram with the corresponding F.
• Detector measures the sum of individual F.
 All wavelengths of light are in-phase and interfere constructively

Low intensity region

An interferogram of light of many wavelength from a broadband IR

source
 How many scans should be used?

SNR ∝ N1/2

Noise level
N =1

N =100 Noise level

 How An Interferogram Becomes A Spectrum?

• Fourier transform is mathematical calculation

• Calculate superposition of sine and cosine waves for
a given function, such as spectrum of IR beam that
hits the detector
• By passing IR radiation through interferometer,
spectrum IR beam is optically transformed into
interferogram
• Detector measures this interferogram
• Fourier transform convert it back to a spectrum
 Instrumental Resolution
• resolution of a spectrometer is a measure of how
well an instrument distinguishes peaks that are
close together
• High resolution (separation of peaks at 2799 &
2800 cm-1) -> instrumental resolution 1 cm-1
• Low resolution (separation of peaks at 2770 &
2800 cm-1) -> instrumental resolution 30 cm-1

Resolution ∝ 1/δ
δ = maximum optical path difference for a scan
 Sample Suggested OPD Mirror
Typical Instrumental Setting for Different Sample Types
resolution (δ/cm) displacement
(cm-1) (Δ/cm)

Solids/liquids 8 or 4 0.125 0.0625

Gases 2 or higher 0.5 0.25

SNR ∝ Resolution
 FTIR Trading Rules
(to maximize spectral quality)

• Relate scanning parameters, spectral quality and

analysis time so to maximize spectral quality and
minimize analysis time.

• Parameters:
SNR,
Resolution (Res),
Analysis time (T),
Number of scans (N)
Trading rule 1: SNR ∝ N1/2

Trading rule 2: SNR ∝ Resolution

Trading rule 3: T ∝ N

Trading rule 4: T ∝ 1/Resolution

FTIR HARDWARE
1. Infrared Sources
• Provide light with which a spectrum is measured.
• Globar, Nernst glower, Nichrome wire, Mercury arc

2. Interefometers
• F = 2vW, hence mirror moves freely and at constant
velocity to ensure accurate F and OPD
• Friction is avoided by having air bearing or mechanical
bearing interferometers
3. Beamsplitters
• Thin film of Ge coated with two IR transparent
windows (KBr)
• Ge has the right thickness to transmit and reflect
some IR radiation
4. IR Detectors
• Detector element converts light intensity to electrical
signal (voltage)
• Type and material of the detector element determine
sensitivity and wavelength range, speed of response
and noise (N) level
• Area of detector element ∝ noise level (< 1mm2)
• Thermal vs Quantum Detectors
 Thermal Detectors
based the conversion of a temperature change,
resulting from high-intensity radiation falling on a
suitable material, into a measurable signal (e.g:
deuterated triglysine sulfate, DTGS)
Advantages Disadvantages

• can be used over a • slow response time

wide range of
• lower sensitivity
wavelengths
(resolution) relative
• operate at room to other types of
temperature.
detectors.
 Quantum Detectors
convert incoming photons directly into an
electrical signal
(e.g: mercury cadmium telluride, MCT)

Advantages Disadvantages
• Fast response • Responsitivity is
• high detectivity wavelength
dependent
• Requires cooling.
 The Computer
• All measured signals are digitized and sent to the computer
where the Fourier transformation takes place.
• To obtain a relative scale for the absorption intensity, a
background spectrum must also be recorded. This is usually a
measurement w/o a sample in the beam.
• A single background measurement can be used for many sample
measurements because this spectrum is characteristic of the
instrument itself.
• This can be compared to the spectrum of a sample in the beam to
determine the “percent transmittance.”
• This technique results in a spectrum which has all of the
instrumental characteristics removed. All spectral features which
are present are strictly due to the sample.
Proper Use of Spectral Processing
 Rules of Spectral Processing
1. Examine original spectrum to decide if it
needs processing. Do not process spectra
automatically
2. Have a clear idea of how processing
logarithm works, the problems it may cause,
and how to avoid them
3. Retain original data
4. Record how, when, and why processing is
performed
 Spectral subtraction
• Used to simplify mixture spectra by removing unwanted
contributions such as water vapor, solvents, CO2, interferents,
impurities, and unknown compounds.
• Two spectra must be plotted with y-axis units that are linearly
proportional to concentration (Abs)
Asample – Aref = Result Absorbance
• Reference features in the spectra being subtracted must be perfect
overlays (have the same width, height, shape and wavenumber
position)
Examples of a spectral subtraction
 Baseline Corrections

offset

Adding/Subtracting appropriate constant from the spectrum to get

the baseline down to zero
Ac = Ai - Amin
Ac = absorbance in baseline-corrected spectrum
Ai = absorbance at any wavelength, i in uncorrected spectrum
Amin = minimum absorbance in uncorrected spectrum
• A function that closely parallels the spectrum baseline is
drawn (line segment endpoint)
• Baseline then subtracted from spectrum

Slope baseline
• Sample too thick
• Light scattering due to large
particles
 Smoothing
• Savitsky-Golay method
• Boxcar smoothing
 Deconvulation

• A technique which enhance resolution of a

spectrum by separating overlapped peaks in the
spectrum