UCB009-CHEMISTRY
Infra-red (IR) spectroscopy
(Vibrational Transitions)
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A brief outline of IR spectroscopy:
➢ Introduction to IR radiation
➢ Molecular vibrations and modes
➢ Hooke’s law: reduced mass and force constant
➢ Factors affecting the vibrational frequency
➢ Principle of IR spectroscopy
➢ Criteria for a molecule to absorb IR radiation
➢ Classification of vibrational transitions in molecules
➢ Features of an IR spectrum
➢ Relationship between wavelength and wavenumber
➢ Why the x-axis of an IR spectrum is expressed in wavenumber
➢ Why does the IR spectrum contain inverted peaks
➢ Vibrational degrees of freedom
➢ IR spectra of CO2 and H2O
➢ Regions in the IR spectrum and their significance
➢ Distinguish between intramolecular and intermolecular hydrogen bonding
➢ Application of IR
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Introduction to IR Radiation:
➢ The light our eyes see is a small part of a broad spectrum of electromagnetic
radiation.
➢ On the immediate high energy side of the visible spectrum lies the ultraviolet,
and on the low energy side is the infrared.
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Introduction to IR Radiation:
The portion of the infrared region most useful for the analysis of organic compounds is
the mid-IR region that is not adjacent to the visible radiation.
IR radiation range
Near-IR (NIR) Mid-IR (MIR) Far-IR (FIR)
0.8-2.5 µm 2.5-15 µm 15-200 µm
800 nm – 2500 nm 2500 nm – 15000 nm 15000 nm – 200000 nm
(4000 cm-1 – 667 cm-1)
Note: Energy associated with the infrared region
is sufficient enough to cause vibrational
transitions only (i.e., molecules get vibrated),
not the electronic transitions in the molecules.
Recall: The electronic transition occurs due to
the photons in the UV-visible region.
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Why do molecules vibrate?
▪ An organic molecule consists of covalent bonds between atoms.
▪ Every covalent bond can be assumed as a spring holding the atoms together.
▪ A spring (i.e. a chemical bond) can undergo both stretching and compression
▪ IR radiation induces vibrational transitions in molecules.
Equilibrium bond length
Compressed covalent bond
Stretched covalent bond
Note: All molecules are not diatomic; they can be triatomic or polyatomic too.
Exercise 1:
True or False: Sodium chloride and Potassium chloride will vibrate
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What are molecular vibrations?
Modes of Vibration:
1- Stretching Vibrations 2- Bending vibrations
symmetrical stretching
scissoring
A- In-plane bending
rocking
Symmetric stretching
asymmetrical stretching
Scissoring Rocking
twisting
b- Out-of-plane bending
wagging
Asymmetric stretching
Energy order: Asymmetric > Symmetric > bending
Twisting Wagging
for IR absorption
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Modes of Vibration: Another representation of directional bond movements
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Do all covalent bonds vibrate at the same frequency?
➢ Recall: All covalent bonds can be assumed as springs holding the atoms together.
Note: The molecule may have more than one type of covalent bond.
➢ During molecular vibrations, the atoms/nuclei of a molecule change their relative
positions whereas, the center of mass of the molecule does not change.
➢ These vibrations can be modeled as harmonic
oscillators, where the restoring force (F) is
Compression
proportional to displacement as per Hooke’s
Law
1 Equilibrium
𝐹 = −𝑘𝑥 𝑜𝑟 𝐸 = 𝑘𝑥 2
2 position
where k: force or spring constant Stretch
x: displacement
E: potential energy
➢ The negative sign denotes that the directions of the restoring force (F) and the
displacement (x) vectors are opposite to each other.
➢ Hence, the energy (E) required to either stretch or compress a given bond in a
molecule is equal/same. UCB009_2425EVESEM
Do all covalent bonds vibrate at the same frequency?
Therefore, based on a simple harmonic oscillator model, the classical vibrational
frequency of a covalent bond can be estimated from Hooke’s law as:
1 𝑘 𝜈 1 𝑘 −1
𝜈= 𝐻𝑧 or 𝜈ҧ = = 𝑐𝑚
2𝜋 𝜇 𝑐 2𝜋𝑐 𝜇
Where:
𝜈 = vibrational frequency (Hz) Where:
k = force constant (Nm-1 or dynes/cm) 𝜈ҧ = wavenumber (cm-1)
𝜇 = reduced mass (kg) c = speed of light (3×1010 cm/s)
𝑀1 × 𝑀2
μ=
𝑀1 + 𝑀2
M1 & M2 = masses of atoms in kg
Note: Fundamental vibrational frequencies are ALWAYS expressed in cm-1
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Factors affecting the vibrational frequency:
1 𝑘 𝜈 1 𝑘 −1
𝜈= 𝐻𝑧 or 𝜈ҧ = = 𝑐𝑚
2𝜋 𝜇 𝑐 2𝜋𝑐 𝜇
If Bond strength (k) increases vibrational frequency
or increases
Reduced mass (µ) decreases
If Bond Strength (k) decreases
or vibrational frequency
Reduced mass (µ) increases decreases
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Effect of force constant on vibrational frequency:
1. Force constant when both atoms are same (reduced mass is same)
Bond Force constant Vibrational frequency
(dynes/cm) (cm-1)
5x105 ~1100 cm-1
10x105 ~1650 cm-1
15x105 ~2200 cm-1
2. Force constant when both atoms are different (when reduced mass is almost similar):
Bond Force constant Vibrational frequency
(dynes/cm) (cm-1)
4.69x105 ~2900 cm-1
6.12x105 ~3600 cm-1
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Exercise 2:
For the following set of covalent bonds, which one has a higher vibrational frequency
• C-C vs C=C
• C-H vs C-D
• C-N vs CN
Hints to solve this exercise:
• Take a critical look at the bond type
• Recall the various parameters in Hooke’s law
• Think how is the vibrational frequency related to these parameters
Exercise 3:
(a) Rank the following bonds in order of increasing stretching frequency (cm-1) in IR spectroscopy:
O-H, C≡N, C-N and C=O
(b) Why C=O stretching occurs at higher frequencies than the stretching of C=C bond?
Hints to solve this exercise:
• Take a critical look at the bond type
• Recall the various parameters in Hooke’s law
• Arrange them in an increasing order (i.e. from lower to higher) vibrational frequency
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Exercise 4:
(a) Calculate the approximate stretching frequency of C-H (cm-1) from the following data:
k = 500 Nm-1, mC = 20 X 10-24 g, mH = 1.6 X 10-24 g. (Ans: 3084 cm-1)
(b) 1H 35Cl gas has a force constant (k) value of 480 N/m. Calculate the fundamental frequency (in
Hz) and its wavenumber (cm-1). (Ans: 8.66 × 1013 Hz, 2888 cm-1)
Hints to solve this exercise:
• At first, see whether the masses of the given atoms are in atomic mass units (a.m.u. i.e.
atomic masses only)
• If given in a.m.u., first convert them into kg using the conversion formula: 1 a.m.u. = 1.66 x
10-27 kg
• If the masses are already provided in grams; convert them into kg.
• Calculate the reduced mass of the given covalent bond in kg.
• Apply Hooke’s law and calculate the vibrational frequency in Hertz (Hz) using given
parameters.
• Very Important Step: Convert the vibrational frequency (in Hz) into wavenumber (cm-1)
by applying another formula (shown earlier).
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Principle of IR spectroscopy:
A molecule will absorb IR radiation when the natural frequency of vibrations of
bond(s) of a molecule is the same as that of the frequency of incident radiation.
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Criteria for a molecule to absorb IR radiation
Changes/fluctuations in the dipole moment
A molecule is said to have a dipole moment when there is a separation of charge between
two atoms in a covalent bond.
Dipole moment Dipole moment of a bond in a molecule
The vibrational motion of the molecule should be accompanied by a change in
(fluctuating) dipole moment, i.e., the dipole moment must change during the vibration.
Why is the fluctuating dipole moment important for IR absorption?
➢ As the bond vibrates, the distance between the
charges increases and decreases, so the dipole
moment also oscillates back and forth
➢ Thus, IR radiation can interact with the
oscillating dipole.
➢ If the IR radiation has the same frequency as
the oscillating dipole, the IR photons will be
absorbed by the molecule
➢ Vibrational transitions will occur
➢ We obtain an IR spectrum of the molecule
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Classification of Vibrational Transitions in Molecules
Vibrational transitions
IR active transitions IR inactive transitions
• a significant change in the dipole moment of a • do not result in any change in the dipole
chemical bond moment
• leads to strong absorption bands e.g. Carbonyl • does not give rise to any absorption band
group e.g., Homonuclear diatomic molecules
Exercise 5:
Find out which of the following molecules are IR active and IR inactive
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