FTIR Lecture Slides
FTIR Lecture Slides
spectroscopy
• Molecular vibrations
• Thermal infrared wavelengths Increasing energy
• Molecular rotations
• Microwave and far-IR wavelengths
~10-23 J
Wavelength
• If there are no available quantized energy levels matching the quantum energy of the incident
radiation, then the material will be transparent to that radiation
Molecular Vibrations
Atomic and molecular vibrations correspond to excited energy levels in quantum mechanics
Excited level
Û DE = hn
Energy
Ground level
The atom is vibrating at The atom is at least partially in an
frequency, ν. excited state.
• For a given frequency of radiation, there is only one value of quantum energy for the photons of that radiation
• Transitions between energy levels occur by absorption, emission and stimulated emission of photons
Absorption
Atoms and molecules can also absorb photons, making a transition from a lower level to a more excited one
Excited level
This photon has
been absorbed
Energy
Ground level
Emission
Before After
Spontaneous
emission
Absorption
Stimulated
emission
In 1916, Einstein showed that another process, stimulated emission, can occur
Molecular Vibrations
When we say a covalent bond between two atoms is of a certain length, we are citing an average because the
bond behaves as if it were a vibrating spring connecting the two atoms
H H
C C
H H
symmetric asymmetric
9 9
Absorption spectra of molecules
1 k ( m1 + m2 )
n=
2pC m1m2
m1, m2 = atomic mass of vibrating atoms
V = wavenumber [cm-1] Let’s consider bond strength, K:
k = force constant (bond strength) [dynes cm-1] A C≡C bond is stronger than a C=C
bond is stronger than a C-C bond
For a single bond, k = 5×105 dynes cm-1 wavenumber, cm-1
For a double bond, k = 10×105 dynes cm-1 C≡C ~2100
For a triple bond, k = 15×105 dynes cm-1 C=C ~1650
C—C ~1200
Due to the reduced mass term, these two bonds of similar strength show up in very different regions of the IR spectrum:
§ The corresponding wavelengths are on the order of 2500-15,000 nm or 2.5 – 15 microns (mm)
§ When a molecule is bombarded with electromagnetic radiation (photons) that match the frequency of one of
these vibrations (IR radiation), it is absorbed and the bonds begin to stretch and bend more strongly (emission
and absorption)
§ When this photon is absorbed the amplitude of the vibration is increased NOT the frequency
IR Spectrum
• The x-axis of the IR spectrum is in units of wavenumbers, n, which is the number of waves per centimeter in units of
cm-1 (Remember E = hn or E = hc/l)
• This unit is used rather than wavelength (microns) because wavenumbers are directly proportional to the energy of
transition being observed
chemists like this, physicists hate it
High frequencies and high wavenumbers equate higher energy
is quicker to understand than
Short wavelengths equate higher energy
C-H
O-H
C=O C-O
stretching
alkenes
O-H aromatic
WAVENUMBER (cm-1)
Basic Functional Group
1. The primary use of the IR spectrometer is to detect functional groups
2. Because the IR looks at the interaction of the EM spectrum with actual bonds, it provides a unique qualitative probe into the
functionality of a molecule, as functional groups are merely different configurations of different types of bonds
3. Since most “types” of bonds in covalent molecules have roughly the same energy, i.e., C=C and C=O bonds, C-H and N-H bonds
they show up in similar regions of the IR spectrum
4. Remember all organic functional groups are made of multiple bonds and therefore show up as multiple IR bands (peaks)
Fingerprint
Region
16
4000 cm-1 2700 cm-1 2000 cm-1 1600 cm-1 400 cm-1
FTIR Spectrum
• The intensity of an IR band is affected by two primary factors:
Whether the vibration is one of stretching or bending
Electronegativity difference of the atoms involved in the bond:
• For both effects, the greater the change in dipole moment in a given vibration or bend, the larger the peak.
• The greater the difference in electronegativity between the atoms involved in bonding, the larger the dipole
moment
• The position of the spectral band is dependent on bond strength and atomic size
• The intensity of the peak results from the efficiency of the coupling; e.g. vibrations that have a large change in
dipole moment create a larger electrical field with which a photon can couple more efficiently
sp C—H 3310-3320
Diethylamine
Do Practice and identify compounds from IR Spectra
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