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Infrared Light
Energy of IR photon insufficient to cause electronic excitation but can cause vibrational or rotational excitation
moment due to vibration or rotation to absorb IR radiation. Homonuclear diatomic molecules will have no IR spectrum. Molecule dipole moment interacts with IR photon electric field. Absorption causes increase in vibration amplitude/rotation frequency.
symmetric stretching
asymmetric stretching
scissoring
wagging
rocking
twisting/torsion
Vibrational Modes: To determine the vibration of polymolecule we need to consider: -motion of the entire molecule in space -rotational motion of the molecule around its centre of gravity -Motion of each atom (individual vibrations). Molecule containing N atoms have 3N degree of freedom
Vibrational coupling :
In addition to the vibrations mentioned above, interaction
between vibrations can occur (coupling) if the vibrating bonds are joined to a single, central atom. Vibrational coupling is influenced by a number of factors; 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 between a stretching vibration and a bending vibration occurs if the stretching bond is one side of an angle varied by bending vibration Coupling is greatest when the coupled groups have approximately equal energies No coupling is seen between groups separated by two or more bonds
Instrumentation: Sources
Instrumentation: Transducers
Michelson interferometer
Fourier Transform
Time Frequency
FT
FTIR advantages
High S/N ratios
Rapid (<10 s)
Reproducible
(a) transparent windows (NaCl/KBr) (b) long pathlength (10 cm) - few molecules Liquids-fill liquid cell (a) solute in transparent solvent - not water (b) short pathlength (0.015-1 mm) Solids-make semi-transparent pellet with KBr
Qualitative Analysis
Step One: Identify
Quantitative Analysis
IR more difficult than UV-VIS complex spectra weak incident beam low sensitivity solvent absorption IR mostly used for rapid qualitative but not quantitative analysis