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IR Spectrum Peak Broadening: Hydrogen Bonding

IR Spectrum Peak Broadening: Hydrogen Bonding

The vibrational frequency of a bond is directly proportional to its bond strength. As a result, stronger bonds vibrate at higher frequencies, while weaker bonds vibrate at lower frequencies. The stretching vibration of the strong O–H bond in alcohols and phenols (very dilute solution or gas phase) appears as a sharp peak at 3600–3650 cm−1.
However, the extent of hydrogen bonding influences the observed stretching frequency and band broadening. Intermolecular or intramolecular...

IR Spectroscopy: Molecular Vibration Overview

IR Spectroscopy: Molecular Vibration Overview

When Infrared (IR) radiation passes through a covalently bonded molecule, the bonds transition from lower to higher vibrational levels. The fundamental vibrational motions that result in infrared absorption can be classified as stretching or bending vibrations.
Stretching vibrations are vibrational motions that occur along the bond line, changing the bond length or distance between two bonded atoms. They are further distinguished as symmetric or asymmetric. In symmetric stretching, the...

IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations

IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations

Identical bonds within a polyatomic group can stretch symmetrically (in-phase) or asymmetrically (out-of-phase). Similar to hydrogen bonding, these vibrations also influence the shape of the IR peak. Generally, asymmetric stretching frequencies are higher than symmetric stretching frequencies. For example, primary amines exhibit two distinct IR peaks between 3300–3500 cm−1 corresponding to the symmetric and asymmetric N-H stretching, while secondary amines exhibit a single...

IR Frequency Region: Alkene and Carbonyl Stretching

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Double bonds in alkenes and carbonyl compounds exhibit stretching frequencies in the diagnostic region of the IR spectrum. In addition, alkenes exhibit vinylic C–H stretching and C–H out-of-plane bending absorptions that are useful for identifying substitution patterns.
Stretching frequencies are affected by several factors, such as resonance, inductive effects, ring strain, dipole moment, and hydrogen bonding. Consequently, the stretching frequency of the carbonyl double bond...

IR Absorption Frequency: Delocalization

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Electron delocalization refers to the distribution of electrons across multiple atoms within a molecule rather than being confined to a single atom or bond. This phenomenon is common in systems with conjugated bonds—structures where alternating single and double bonds allow π-electrons to move freely across the network. The movement of electrons stabilizes the molecule and can affect various chemical properties, including vibrational frequencies observed in IR spectroscopy.
In IR...

IR Frequency Region: X–H Stretching

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In IR spectroscopy, signals produced by the X−H bonds (such as C−H, O−H, or N−H) can be observed in the frequency range of 2700–4000 cm–1. The C−H stretching vibration forms sharp bands in the region 2850–3000 cm–1. The presence of the O−H stretching vibration leads to the forming of an absorption band in the frequency range 3650–3200 cm−1. At the same time, N−H stretching can be confirmed by absorption bands in...

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Related Experiment Video

Updated: Apr 27, 2026

Measurement and Analysis of Atomic Hydrogen and Diatomic Molecular AlO, C2, CN, and TiO Spectra Following Laser-induced Optical Breakdown

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Published on: February 14, 2014

Alcohol dimers--how much diagonal OH anharmonicity?

Franz Kollipost¹, Kim Papendorf, Yu-Fang Lee

¹Georg-August-Universität Göttingen, Institut für Physikalische Chemie, Tammannstr. 6, 37077 Göttingen, Germany. msuhm@gwdg.de.

Physical Chemistry Chemical Physics : PCCP

|June 26, 2014

Summary

This summary is machine-generated.

Hydrogen bonding significantly increases the anharmonicity of alcohol OH bonds, drastically reducing the infrared intensity ratio between overtone and fundamental transitions. This effect is more pronounced with increased alkyl substitution.

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Area of Science:

Physical Chemistry
Spectroscopy
Computational Chemistry

Background:

Hydrogen bonding influences molecular vibrations, particularly the hydroxyl (OH) stretching mode in alcohols.
Previous studies have observed shifts in OH stretching frequencies due to hydrogen bonding, but anharmonic effects are less understood.
Infrared (IR) spectroscopy is a key technique for probing molecular vibrations and hydrogen bond strength.

Purpose of the Study:

To quantify the changes in OH bond anharmonicity and IR intensity ratios in isolated alcohol dimers upon hydrogen bonding.
To compare experimental findings with anharmonic vibrational predictions.
To evaluate the accuracy of quantum chemistry methods in describing hydrogen-bonded alcohol vibrations.

Main Methods:

Fourier Transform Infrared (FTIR) spectroscopy of supersonic slit jet expansions to study isolated alcohol dimers.
Analysis of the OH stretching mode's fundamental and overtone transitions.
Comparison with theoretical calculations using vibrational second-order perturbation theory and harmonic quantum chemistry.

Main Results:

Diagonal anharmonicity of the OH bond increases by 15-18% upon hydrogen bonding, with greater increases for larger alkyl substituents.
The overtone/fundamental IR intensity ratio drops significantly from ~0.1 for isolated alcohols to 0.004-0.001 for hydrogen-bonded OH groups.
Vibrational second-order perturbation theory provides semiquantitative agreement, while harmonic predictions are insufficient; anharmonic cross terms are crucial.

Conclusions:

Hydrogen bonding substantially enhances OH bond anharmonicity and suppresses overtone intensities in alcohols.
Accurate theoretical descriptions require high-level electronic structure theory and inclusion of anharmonic cross terms.
Matrix isolation data complements supersonic jet expansion results, providing insights into matrix effects on hydrogen bond donor vibrations.