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Fundamental Principles

This document provides information about FT-IR spectroscopy. It discusses the infrared region and the types of molecular information that can be obtained from each region. Near-IR provides information about vibrational and rotational transitions, mid-IR provides information about fundamental vibrational levels, and far-IR provides information about rotational energy levels. The document also summarizes the principles of IR spectroscopy, including how IR radiation causes molecular absorption and creates a molecular fingerprint. Key terms like fundamental vibrations, overtones, and coupling are defined. Advantages of FT-IR like high resolution and sensitivity are highlighted.

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114 views31 pages

Fundamental Principles

This document provides information about FT-IR spectroscopy. It discusses the infrared region and the types of molecular information that can be obtained from each region. Near-IR provides information about vibrational and rotational transitions, mid-IR provides information about fundamental vibrational levels, and far-IR provides information about rotational energy levels. The document also summarizes the principles of IR spectroscopy, including how IR radiation causes molecular absorption and creates a molecular fingerprint. Key terms like fundamental vibrations, overtones, and coupling are defined. Advantages of FT-IR like high resolution and sensitivity are highlighted.

Uploaded by

Kassim
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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FT-IR 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


 When IR radiation is passed through a sample, some of
the infrared radiation is absorbed by the sample and
some of it is transmitted.

 The resultant spectrum represents the molecular


absorption and transmission, thus creating a molecular
fingerprint of the sample.

 No two unique molecular structures produce the same


infrared spectrum.

 Useful for several types of analysis.


IR Spectroscopy
• A method of “Seeing the unseeable”
• An instrumentally aided study of the interactions
between matter (sample being analyzed) and
energy (IR radiation)
• Concerned with the study of absorption of infrared
radiation, which causes vibrational transition in the
molecule.
• Also known as vibrational spectroscopy.
• Used in structure elucidation to determine the
functional groups.
Energy of molecule = Electronic + Vibrational + Rotational
Principles
• Molecules are made up of chemically bonded atoms.
The movement of atoms and the chemical bonds is like
a spring and balls (vibration)

• This characteristic vibration is called Natural frequency


of vibration.
• When infrared radiation is applied, it causes the
vibration between the atoms of the molecules:
Applied IR frequency = Natural frequency of vibration

• Absorption of IR radiation takes place and a peak is


observed.

• Different functional groups absorb characteristic


frequencies of IR radiation. Hence gives the
characteristic peak value.

• IR spectrum of a chemical substance is a finger print of


a molecule for its identification.
Absorption of IR Light
Correct wavelength of radiation
 The natural frequency of vibrations of some s of a
molecule is the same as that of incident radiation.

Change in dipole moment, µ


 A molecule can only absorb IR radiation when its
absorption causes a change in its electric dipole
 A molecule is said to have an electric dipole when there
is a slight positive and a slight negative charge on its
component of atoms.
DIPOLE MOMENT (µ)
µ=Qxr Q = charge
r = distance between charges

 Asymmetrical distribution of e- in a bond renders the


bond polar
 A result of electronegativity difference
 µ changes upon vibration due to changes in r
 Change in µ with time is necessary for a molecule to
absorb IR radiation
 The repetitive changes in µ makes it possible for polar
molecules to absorb IR radiation
 Symmetrical molecules do not absorb IR radiation
(O2, F2, H2, Cl2)

 Diatomic molecules with dipole moment are IR-active


(HCl, HF, CO, HI)

 Molecules with more than two atoms may or may not


be IR active depending on whether they have
permanent net dipole moment
•Absorption of IR light causes changes in the
vibrational motions of a molecule.
•The different vibrational modes available to a
molecule include stretching and bending modes.

•The vibrational modes of a molecule are quantized,


so they occur only at specific frequencies which
correspond to the frequency of IR light.
11
Molecular
Vibrations

Fundamental Non-
Vibrations fundamental
Vibrations

Stretching Bending Over Tones,


Vibration Vibration Combination
Tones,
Fermi
In-plane Out Of Plane Resonance
Symmetric Asymmetric
Bending Bending

Scissoring Rocking Wagging Twisting


FUNDAMENTAL VIBRATIONS
Arise from ground state to lowest excitation state
Stretching vibration:
• Vibration or oscillation along the line of bond
• Change in bond length
• Occurs at higher energy: 4000-1250 cm-1
• TWO types:
i. Symmetrical stretching
ii. Asymmetrical stretching
Symmetrical stretching:
Two bonds increase or decrease in length
simultaneously.

H
Asymmetrical stretching
• one bond length is increased and the other is
decreased.

H
Bending vibrations
• Vibration or oscillation not along the line of
bond
• These are also called deformations because
bond angle is altered
• Occurs at low energy: 1400-666 cm-1
• TWO types:
i. In plane bending: scissoring, rocking
ii. Out of plane bending: wagging, twisting
In plane bending
i. Scissoring:
• This is an in plane blending
• 2 atoms approach each other
• Bond angles are decrease

H
ii. Rocking:
• Movement of atoms take place in the same
direction.

H
Out plane bending
i. Wagging:
• Two atoms move to one side of the plane. They
move up and down the plane.

ii. Twisting:
• One atom moves above the plane and another
atom moves below the plane.
NON-FUNDAMENTAL VIBRATIONS
OVER TONES: FERMI
COMBINATION •Excitation from RESONANCE:
BANDS/TONES: ground state to •COUPLING btw
Weak bands that higher energy fundamental
appear states vibrations &
occasionally at •Observed at overtones
frequencies that integral multiples /combination
are sum/difference of the frequency tones.
of two or more of a strong band. • Often observed
fundamental in carbonyl
bands. E.g:
compounds
carbonyl group.
COUPLED INTERACTIONS

Interactions between vibrations can occur (Coupling) if the


vibrating bonds are joined to a single, central atom.

This is because there is mechanical coupling interaction


between the oscillators.

Example:
C=O (both symmetric and asymmetric stretching vibrations)
REQUIREMENTS FOR COUPLING
The vibrations must be of the same symmetry
species if interaction is to occur

Strong coupling of stretching vibrations occurs


when there is a common atom between the two
vibrating bonds.

Coupling of bending vibrations occurs when there


is a common bond between vibrating groups.
• Coupling is greatest when the coupled groups
have approximately equal energies

• Coupling between a stretching vibration and a


bending vibration occurs if the stretching
bond is one side of an angle varied by
bending vibration.

• No coupling is seen between groups


separated by two or more bonds
c Greater
coupling

C c c
Less coupling

no coupling
Hook’s Law
Gives the relation between frequency of
oscillation , atomic mass and force constant of
the bond .
Natural vibrational frequency, v

C = velocity of light
K = force constant(measures bond strength)
μ= reduced mass
FACTORS AFFECTING THE FREQUENCY OF
THE IR ABSORPTION

THE RELATIVE MASS OF THE


ATOMS: heavier the atoms lower is
the vibration frequency of the bond
between them.

THE FORCE CONSTANT OF


THE BONDS: Stronger the bond
higher is the vibration frequency.
Force constant for chemical bonds
Advantages of FTIR
• Very high resolution (< 0.1 cm –1 )
- governed by the distance movable mirror travels

• Very high sensitivity (nanogram quantity)


can be coupled with GC analysis (–> measure IR spectra in gas-phase)

• High S/N ratios - high throughput


Few optics, no slits mean high intensity of light

• Rapid (<10 s)

• Reproducible and

• Inexpensive
– Multiplex advantage (Fellgett advantage): All source
wavelengths are measured simultaneously in an
interferometer, whereas in a dispersive spectrometer they
are measured successively. A complete spectrum can be
collected very rapidly and many scans can be averaged in
the time taken for a single scan of a dispersive
spectrometer.
– Throughput advantage (Jacquinot advantage): For the
same resolution, the energy throughput in an
interferometer can be higher than in a dispersive
spectrometer, where it is restricted by the slits. FTIR has the
ability to achieve the same signal-to-noise ratio as a
dispersive instrument in a much shorter time.
– Calibration advantage: The wavenumber scale of an
interferometer is derived from a HeNe laser that acts as an
internal reference for each scan. The wavenumber of this
laser is known very accurately and is very stable. As a result,
the wavenumber calibration of interferometers is much
more accurate and has much better long term stability than
the calibration of dispersive instruments.
– Negligible stray light: Because of the way in which the
interferometer modulates each source wavelength. There is
no direct equivalent of the stray light found in dispersive
spectrometers.
– No discontinuities: Because there are no grating or filter
changes, there are no discontinuities in the spectrum.

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