Factors affecting the IR absorption band frequencies
The position of absorption bands in an infrared (IR) spectrum—measured as frequency or wavenumber (cm⁻¹)—
is influenced by several molecular and environmental factors. These factors determine how strongly and at what
frequency a bond vibrates when exposed to infrared radiation. The absorption frequency primarily depends on
the mass of the atoms, bond strength, and the surrounding chemical environment. Understanding these
factors is essential for accurate interpretation of IR spectra and for identifying functional groups in organic and
inorganic compounds.
1- Bond Order Effect
Bond order refers to the number of chemical bonds between a pair of atoms. As the bond order increases (i.e.,
single → double → triple bond), the bond becomes stronger and stiffer, leading to higher vibrational
frequencies in the IR spectrum.
General Trend:
Triple bond > Double bond > Single bond
This is because a stronger bond (with higher force constant) requires more energy to stretch, so it absorbs IR
radiation at a higher wavenumber.
Bond Type Approximate IR Frequency
C–C (single bond) Not easily IR active
C=C (double bond) ~1650 cm⁻¹
C≡C (triple bond) ~2100–2260 cm⁻¹
2- Electronic Effect
The electronic effect refers to the influence of electron-donating or electron-withdrawing groups on
the bond strength and polarity of nearby bonds. These effects can shift the IR absorption frequency
either higher or lower, depending on how they affect electron distribution.
Types of Electronic Effects:
(a) Inductive Effect
Caused by electronegative atoms or groups that pull electron density through sigma bonds. This increases
bond polarity and usually increases the absorption frequency.
Example:
C=O in acetone ≈ 1715 cm⁻¹
C=O in trifluoroacetone (with –CF₃ group) ≈ 1750 cm⁻¹
→ The electron-withdrawing –CF₃ group increases the frequency.
(b) Resonance (Mesomeric) Effect
Involves delocalization of electrons, which reduces bond order and lowers the absorption frequency.
Example: C=O in acetone (no conjugation) ≈ 1715 cm⁻¹
C=O in α,β-unsaturated ketone (with conjugation) ≈ 1685 cm⁻¹
→ Resonance with the C=C double bond weakens the C=O bond.
3- Hybridization effect
The hybridization of an atom directly affects the bond strength and, consequently, the vibrational frequency
observed in IR spectroscopy. This is especially noticeable in C–H stretching vibrations. The more s-character in
the hybrid orbital, the stronger and shorter the bond becomes. Stronger bonds vibrate at higher frequencies.
Order of s-character:
sp hybridized: 50% s-character
sp² hybridized: 33% s-character
sp³ hybridized: 25% s-character
Resulting Frequency Trend:
C–H (sp) > C–H (sp²) > C–H (sp³)
Simple Examples:
Alkyne (–C≡C–H, sp): C–H stretch ≈ 3300 cm⁻¹
Alkene (=C–H, sp²): C–H stretch ≈ 3100 cm⁻¹
Alkane (–C–H, sp³): C–H stretch ≈ 2900 cm⁻¹
These differences help in distinguishing between types of hydrocarbons and carbon centers in an unknown
sample.
4- Ring Strain Effect
What is Ring Strain?
Ring strain arises when the bond angles in a cyclic compound deviate from the ideal 109.5° tetrahedral angle,
especially in small rings like 3- or 4-membered rings. This strain causes the bonds—particularly the carbonyl
(C=O) bond—to become more rigid and tense.
Cyclopropane (3-membered ring):
Internal bond angle = 60°
Much smaller than 109.5° → causes severe angle strain
Bonds are “bent” or “banana bonds” to try to relieve strain
Cyclobutane (4-membered ring):
Internal bond angle ≈ 90°
Still much smaller than 109.5° → still strained
Cyclopentane (5-membered ring):
Internal angle ≈ 108°
Very close to 109.5° → less strain
Cyclohexane (6-membered ring):
Can adopt a chair conformation
Achieves almost perfect 109.5° angles → no angle strain
Compound Ring Size C=O IR Frequency (cm⁻¹)
Cyclopropanone 3-membered ~1850 cm⁻¹
Cyclobutanone 4-membered ~1780 cm⁻¹
Cyclopentanone 5-membered ~1745 cm⁻¹
Cyclohexanone 6-membered ~1715 cm⁻¹
Trend: As the ring becomes smaller, the strain increases, and the C=O absorption shifts to a higher frequency.
5- Hydrogen Bonding Effect
Hydrogen bonding has a significant influence on the position and shape of certain IR absorption bands, especially
those involving –OH, –NH, and –COOH groups.
Red Shift (Lower Frequency): Hydrogen bonding weakens the bond involved (e.g., O–H or N–H), causing it to
vibrate at a lower frequency.
Broadening of the Band: The hydrogen bond varies in strength and geometry, which leads to broad and wide
absorption bands in the IR spectrum.
Examples:
Alcohols:
Free –OH (no H-bonding) in the gas phase absorbs around 3650 cm⁻¹ (sharp peak).
Hydrogen-bonded –OH in liquid alcohol absorbs around 3200–3400 cm⁻¹ (broad peak). Carboxylic Acids:
Strong intramolecular H-bonding causes a very broad O–H stretch around 2500–3000 cm⁻¹. Amines:
–NH₂ group shows two bands (symmetric and asymmetric) in 3300–3500 cm⁻¹ region, which become broader
when hydrogen bonding occurs.
6- Solvent effect
The solvent used during an IR measurement can affect the position (frequency) and shape (broadening) of
absorption bands. This happens because solvents can interact with the solute molecules through dipole–dipole
interactions or hydrogen bonding, especially with polar functional groups.
Polar solvents (like water, methanol, ethanol) can form hydrogen bonds with –OH or –NH groups in the
compound.
→ This lowers the stretching frequency and broadens the IR peak.
Non-polar solvents (like hexane or carbon tetrachloride) interact weakly.
→ Little to no change in the absorption frequency.
Examples:
–OH Stretching in alcohol: In gas phase (no solvent): sharp peak near 3650 cm⁻¹ In liquid (with H-bonding):
broad peak around 3200–3400 cm⁻¹
C=O Stretching in acetone: In non-polar solvent (hexane): ~1715 cm⁻¹ In polar solvent (water): shifted to lower
frequency (~1700 cm⁻¹) due to dipole interactions
→ Polar solvents tend to shift absorption bands to lower frequencies and broaden them due to hydrogen bonding
and dipole interactions, especially for –OH, –NH, and C=O groups.
7- Isotopic Substitution
Isotopic substitution means replacing one atom in a molecule with another atom of the same element but a
different mass (isotope). Since IR absorption frequency depends on the mass of atoms involved, changing to a
heavier isotope lowers the frequency of the vibration. A heavier isotope increases μ, so the vibrational frequency
decreases.
Example:
C–H bond absorbs at ~2900 cm⁻¹ Replace H (mass = 1) with D (deuterium, mass = 2)
→ C–D bond absorbs at ~2100 cm⁻¹
8- Temperature effect
Temperature can influence the shape, intensity, and sometimes the position of IR absorption bands. As
temperature increases: Molecules vibrate more vigorously. Bond lengths increase slightly due to thermal
expansion. Anharmonicity (deviation from ideal vibration) becomes more pronounced.
Main Effects:
a- Broadening of Peaks: Higher temperature causes peaks to become wider due to increased molecular motion.
b- Slight Shift in Frequency: Some bands may show a small red shift (toward lower wavenumbers) as the bond
becomes slightly weaker.
c- Change in Intensity: Peak intensity may change slightly due to changes in population of vibrational energy
levels.
Example:
O–H Stretching in Water: At room temperature, the O–H stretching band appears broad around 3200–3400 cm⁻¹.
At higher temperatures, the peak becomes broader and may shift slightly due to increased hydrogen bond
disruption.
