Spectroscopy

Fourier Transform Infrared (FT-IR) Spectroscopy

Theory and Applications
THE ELECTROMAGNETIC SPECTRUM
GAMMA RAYS X RAYS UV VISIBLE

INFRARED

Introduction to FTInfrared Spectroscopy

What

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is infrared spectroscopy? Theory of FT-IR FT-IR Advantages? New FT/IR4000-6000Series

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What is Infrared?
Infrared radiation lies between the visible and microwave portions of the electromagnetic spectrum. Infrared waves have wavelengths longer than visible and shorter than microwaves, and have frequencies which are lower than visible and higher than microwaves. The Infrared region is divided into: near, mid and far-infrared. * Near-infrared refers to the part of the infrared spectrum that is closest to visible light and far-infrared refers to the part that is closer to the microwave region. * Mid-infrared is the region between these two. The primary source of infrared radiation is thermal radiation. (heat) It is the radiation produced by the motion of atoms and molecules in an object. The higher the temperature, the more the atoms and molecules move and the more infrared radiation they produce. Any object radiates in the infrared. Even an ice cube, emits infrared.

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What is Infrared? (Cont.)

Humans, at normal body temperature, radiate most strongly in the infrared, at a wavelength of about 10 microns (A micron is the term commonly used in astronomy for a micrometer or one millionth of a meter). In the image to the left, the red areas are the warmest, followed by yellow, green and blue (coolest). The image to the right shows a cat in the infrared. The yellow-white areas are the warmest and the purple areas are the coldest. This image gives us a different view of a familiar animal as well as information that we could not get from a visible light picture. Notice the cold nose and the heat from the cat's eyes, mouth and ears.

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Infrared Spectroscopy
The bonds between atoms in the molecule stretch and bend, absorbing infrared energy and creating the infrared spectrum.

Symmetric Stretch

Antisymmetric Stretch

Bend

A molecule such as H2O will absorb infrared light when the vibration (stretch or bend) results in a molecular dipole moment change

Energy levels in Infrared Absorption

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hn Infrared Absorption and Emission n 3 n 2 n 1 n

0

Excited states

h(n1 n0 )

h(n2 - n1) (overtone)

h(n1 - n0)

Ground (vibrational) 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.

Infrared Spectroscopy
A molecule can be characterized (identified) by its molecular vibrations, based on the absorption and intensity of specific infrared wavelengths.

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Infrared Spectroscopy
For isopropyl alcohol, CH(CH3)2OH, the infrared absorption bands identify the various functional groups of the molecule.

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Capabilities of Infrared Analysis

Identification and quantitation of organic solid, liquid or gas samples. Analysis of powders, solids, gels, emulsions, pastes, pure liquids and solutions, polymers, pure and mixed gases. Infrared used for research, methods development, quality control and quality assurance applications. Samples range in size from single fibers only 20 microns in length to atmospheric pollution studies involving large areas.

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Applications of Infrared Analysis

Pharmaceutical research Forensic investigations Polymer analysis Lubricant formulation and fuel additives Foods research Quality assurance and control Environmental and water quality analysis methods Biochemical and biomedical research Coatings and surfactants Etc.

Comparison Beetween Dispersion Spectrometer and FTIR

To separate IR light, a grating is used. Grating Slit Detector

Spectroscopy

Dispersion Spectrometer
In order to measure an IR spectrum, the dispersion Spectrometer takes several minutes. Also the detector receives only a few % of the energy of original light source.

Sample

Light source

To select the specified IR light, A slit is used.

Fixed CCM

An interferogram is first made by the interferometer using IR light.

Detector

FTIR
In order to measure an IR spectrum, FTIR takes only a few seconds. Moreover, the detector receives up to 50% of the energy of original light source. (much larger than the dispersion spectrometer.)

B.S. Sample Moving CCM IR Light source

The interferogram is calculated and transformed into a spectrum using a Fourier Transform (FT).

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The Principles of FTIR Method

Interferogram is made by an interferometer.

Sample Interferogram is transformed into a spectrum using a FT.

BKG SB Sample/BKG 3000 2000 [cm-1] %T 1000

Sample SB

3000

2000 [cm-1]

1000

IR spectrum 3000 2000 1000 [cm-1]

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seminar IR light FTIR source

IR Light Source

Intensity Distribution and Temperature Dependency versus Wavelength of Black Body Radiation Energy
105 104 103 102 10 1 10-1 10-2 300K 10-3 200K 0.1 0.2 0.5 1 2 5 10 20 50 100 1000K

6000K
4000K

2000K

500K

10-4
Wavelength l / mm

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FTIR seminar

FT Optical System Diagram

Light source

He-Ne gas laser

(ceramic) Beam splitter Movable mirror Sample chamber

(DLATGS) Fixed mirror Interferometer Detector

 Movable mirror Opposite-phase interference wave shape

Signal strength

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FTIR seminar

Interference of two beams of light

Movable mirror Fixed mirror Movable mirror Same-phase interference wave shape

-2l

-l

2l

Fixed mirror
(X)

Continuous phase shift

Fixed mirror Movable mirror

Same-phase interference wave shape

-2l
l

-l

2l

Interference pattern of light manifested by the optical-path difference

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FTIR seminar

Interference is a superpositioning of waves

Relationship between light source spectrum and the signal output from interferometer
Light source spectrum I Signal output from interference wave

(a)

Monochromatic light z

Wavenumber

Time t

(b)

Dichroic light

SAz

Wavenumber (c) Continuous spectrum light

I(t)

Time t

b (u)

Wavenumber

Time t All intensities are standardized.

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FTIR seminar

Sampling of an actual interferogram

Interferometer interferogram

Output of a Laser interferometer

Primary interferometer interferogram that was sampled Optical path difference x

Single strength

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Fourier Transform

Fourier transform

SB

Optical path difference[x]

4000

Wavenumber[cm-1]

400

(Interferogram)

(Single beam spectrum)

Time axis by FFT

Wavenumber

D* (l, f) (cmHz1/2W-1)

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FTIR seminar

Detector Properties

1010

MCT Operates at the temperatur of liquid nitrogen

109 TGS Operates at room temperature

108
4000 Wavenumber[cm-1]

600

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FT-IR Advantages and Disadvantages

1.Better sensitivity and brightness - Allows simultaneous measurement over the entire wavenumber range - Requires no slit device, making good use of the available beam 2.High wavenumber accuracy - Technique allows high speed sampling with the aid of laser light interference fringes - Requires no wavenumber correction - Provides wavenumber to an accuracy of 0.01 cm-1 3. Resolution - Provides spectra of high resolution 4. Stray light - Fourier Transform allows only interference signals to contribute to spectrum. Background light effects greatly lowers. - Allows selective handling of signals limiting intreference 5. Wavenumber range flexibility - Simple to alter the instrument wavenumber range

CO2 and H2O sensitive

FT-IR Advantages
Fellgett's (multiplex) Advantage
FT-IR collects all resolution elements with a complete scan of the interferometer. Successive scans of the FTIR instrument are coadded and averaged to enhance the signal-to-noise of the spectrum.

Spectroscopy

Theoretically, an infinitely long scan would average out all the noise in the baseline.
The dispersive instrument collects data one wavelength at a time and collects only a single spectrum. There is no good method for increasing the signal-to-noise of the dispersive spectrum.

FT-IR Advantages
Connes Advantage
an FT-IR uses a HeNe laser as an internal wavelength standard. The infrared wavelengths are calculated using the laser wavelength, itself a very precise and repeatable 'standard'. Wavelength assignment for the FT-IR spectrum is very repeatable and reproducible and data can be compared to digital libraries for identification purposes.

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FT-IR Advantages
Jacquinot Advantage
FT-IR uses a combination of circular apertures and interferometer travel to define resolution. To improve signal-to-noise, one simply collects more scans. More energy is available for the normal infrared scan and various accessories can be used to solve various sample handling problems. The dispersive instrument uses a rectangular slit to control resolution and cannot increase the signal-tonoise for high resolution scans. Accessory use is limited for a dispersive instrument.

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FT-IR Application Advantages

Opaque or cloudy samples

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Energy limiting accessories such as diffuse reflectance or FTIR microscopes

High resolution experiments (as high as 0.001 cm-1 resolution) Trace analysis of raw materials or finished products Depth profiling and microscopic mapping of samples Kinetics reactions on the microsecond time-scale Analysis of chromatographic and thermogravimetric sample fractions

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FT-IR Terms and Definitions

Resolution (common definition) The separation of the various spectral wavelengths, usually defined in wavenumbers (cm-1). A setting of 4 to 8 cm-1 is sufficient for most solid and liquid samples. Gas analysis experiments may need a resolution of 2 cm-1 or higher. Higher resolution experiments will have lower signal-to-noise.

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FT-IR Terms and Definitions

Resolution FT/IR Case A spectrum is said to be collected at a resolution of 1 cm-1 if 4 data points are collected within each spectral interval of 1 cm-1 . In order to acquire a spectrum at higher, an increased number of data points is needed, requiring a longer stroke of the moving mirror. For higher resolution instruments an aperture is needed in order to improve parallelism within interferometer.

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FT-IR Terms and Definitions

Apodization - a mathematical operation to reduce unwanted oscillation and noise contributions from the interferogram and to avoid aberrations coming from the finite nature of real (non theoretical interferograms). Common apodization functions include Beer-Norton, Cosine and Happ-Genzel.

Apodization

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FT-IR Terms and Definitions

Scan mode - Either single beam or ratio. Single beam can be a scan of the background (no sample) or the sample. Ratio mode always implies the sample spectrum divided by, or ratioed against, the single beam background.

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FT-IR Terms and Definitions

Scan(s) - a complete cycle of movement of the interferometer mirror. The number of scans collected affects the signal-to-noise ratio (SNR) of the final spectrum. The SNR doubles as the square of the number of scans collected; i.e. 1, 4, 16, 64, 256, . Scan speed or optical path velocity - the rate at which the interferometer mirror moves. For a DTGS detector, the SNR decreases as the scan speed increases. Scan range - spectral range selected for the analysis. The most useful spectral range for mid-infrared is 4000 to 400 cm-1.

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New Features of FTIR4000-6000Series

The highest S/N ratio in the world, 50,000:1 (FT/IR-6300) (Over sampling with 24-bit ADC) DSP-driven interferometer and new ADC (18-bit to 24-bit) Digital control of the moving mirror drive using an advanced high speed digital signal processor (DSP) technology
The outstanding performance of the ADC (Analog-to digital converter) and DSP (Digital signal processor) allows very rapid and accurate correction for the effects of velocity and position errors.

Autoalignment for all models (The interferometer optics can always be aligned by the PC) In addition to proven technology for Rapid scanning and vacuum capabilities; a Step scan capability enables time-resolved studies similar to research models by Nicolet, Bruker and Bio-Rad. IR imaging with IMV-4000 multi-channel microscope for all models (Rapid scanning with a linear array MCT detector ) PC communication and control using USB Aperture of 7.1, 5.0, 3.5, 2.5, 1.8, 1.2, 0.9, 0.5 mm diameter for FT/IR-4100/4200 Spectra Manager II (cross-platform software suite for JASCO spectroscopy systems) (Spectra Manager CFR: 21 CFR Part 11 compliance) Research model capability (Upgradeable wavelength extension, high resolution, step scan) Improved Water Vapor and CO2 Compensation

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FTIR4000 Series
FT/IR-4100 FT/IR-4200
No additional optics for IR microscope interface Standard apertures for optimum S/N and resolution capability Easy replacement of light source and detector

Microscope

Polymer shell Improved instrument design Compact size Sample compartment with same size as a higher class model

Aperture

FT/IR-400 Plus

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FTIR4000 Series Purge System

Instrument purge is standard for all models of the FT/IR-4000 Series.
N2gas inlet

Control valve FT/IR-4000 Series purge design

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S/N ratio (Oversampling system)

Voice Coil Conventional method FT/IR-4000 & 6000 series Voice Coil
DAC DSP Accurate mirror drive And reduce flutter at low wavenumber range.

Analog circuit

ADC

Pre-amp.

Pre-amp.

Photo coupler

Photo coupler

Clock
24-bit AD

HeNe laser
Find the zero crossings, then interpolate a matching set of IR data points.

HeNe laser
Over sampling method
Reduction of high frequency noise by over sampling with a 16 times greater number of sampling points enables improvement of the S/N ratio.

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FTIR6000 Series
- Upgradeability - Wide wavenumber range - Full vacuum capability - Step scan upgrade

FT/IR-6100 / 6200 / 6300

Microscope FT-Raman

Polymer shell Improved instrument design Compact size

FT/IR-600Plus

FT/IR-6000 Series Optical design

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FTIR6000 Series Purge/Vacuum System

N2gas inlet

Instrument purge is standard for all models of the FT/IR-6000 Series.

Purge control valve front side

FT/IR-6000 Series purge design