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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 Spectroscopy: Hooke's Law Approximation of Molecular Vibration

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration

A covalently bonded heteronuclear diatomic molecule can be modeled as two vibrating masses connected by a spring. The vibrational frequency of the bond can be expressed using an equation derived from Hooke's law, which describes how the force applied to stretch or compress a spring is proportional to the displacement of the spring. In this case, the atoms behave like masses, and the bond acts like a spring.
According to Hooke's law, the vibrational frequency is directly proportional to the...

Applications of IR Spectroscopy: Overview

Applications of IR Spectroscopy: Overview

The non-destructive nature and ability to provide valuable chemical information make IR spectroscopy a versatile technique with broad applications in various scientific and industrial fields. IR spectroscopy is commonly used to identify and characterize organic and inorganic compounds. It provides information about the functional groups present in a molecule and the bonding between atoms. This helps in the structural elucidation of compounds during organic synthesis, pharmaceutical research,...

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 stretching vibration...

IR Absorption Frequency: Delocalization

IR Absorption Frequency: Delocalization

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 spectroscopy,...

IR Absorption Frequency: Hybridization

IR Absorption Frequency: Hybridization

Hydrocarbons such as alkanes, alkenes, and alkynes show characteristic C–H stretching absorption bands. These IR stretching frequencies depend on the hybridization of the involved carbon atom and can be explained in terms of the s character of each hybridized atomic orbital.
Among the sp, sp2, and sp3 hybridized orbitals, sp orbitals have the maximum s character (50%). Consequently, the electrons are held more closely to the nucleus, resulting in stronger and shorter C–H bonds that stretch at a...

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Related Experiment Video

Updated: Jun 27, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization

Published on: August 6, 2018

Multilevel vibrational coherence transfer and wavepacket dynamics probed with multidimensional IR spectroscopy.

Matthew J Nee¹, Carlos R Baiz, Jessica M Anna

¹Department of Chemistry, University of Michigan, 930 N. University Ave., Ann Arbor, Michigan 48109, USA.

The Journal of Chemical Physics

|December 3, 2008

Summary

Multidimensional infrared spectroscopy reveals excited vibrational coherences and coherence transfer in dimanganese decacarbonyl. This technique uncovers slow dynamics and intramolecular interactions influencing molecular dephasing.

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Area of Science:

Physical Chemistry
Spectroscopy
Molecular Dynamics

Background:

Vibrational coherences are crucial for understanding molecular dynamics.
Previous spectroscopic methods lacked the resolution to fully characterize excited state coherences and transfer pathways.
Dimanganese decacarbonyl (Mn2(CO)10) presents a complex multilevel vibrational system suitable for advanced spectroscopic investigation.

Purpose of the Study:

To investigate excited vibrational state coherences and coherence transfer in Mn2(CO)10 using MDIR spectroscopy.
To identify new signatures of coherence transfer and analyze their frequency dependence.
To explore the role of intramolecular interactions and orientational dynamics in dephasing processes.

Main Methods:

Utilized multidimensional infrared (MDIR) spectroscopy to probe Mn2(CO)10 in cyclohexane solution.
Analyzed the waiting-time dependence of cross-peak amplitudes to identify coherence transfer signatures.
Resolved individual excited vibrational coherences for detailed analysis of frequency-frequency correlation functions.

Main Results:

Observed fully resolved excited vibrational state coherences with slow decay constants (0.25-0.50 ps(-1)).
Identified a novel signature of coherence transfer characterized by temporally modulated cross-peak amplitudes at multiple frequencies.
Provided direct measurements of frequency-frequency correlation functions for excited states relative to each other and the ground state.

Conclusions:

MDIR spectroscopy offers unprecedented insight into excited state dynamics and coherence transfer.
The observed slow dynamics and multiple modulation frequencies highlight the significance of intramolecular interactions.
The study underscores the power of 3D spectroscopy in revealing slow dynamics and dephasing mechanisms involving dark or low-frequency modes.