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Related Concept Videos

IR Spectroscopy: Molecular Vibration Overview01:24

IR Spectroscopy: Molecular Vibration Overview

4.3K
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...
4.3K
IR Frequency Region: X–H Stretching01:24

IR Frequency Region: X–H Stretching

1.3K
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...
1.3K
IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration01:16

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration

2.7K
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...
2.7K
IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations01:08

IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations

1.7K
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...
1.7K
IR Frequency Region: Alkene and Carbonyl Stretching01:29

IR Frequency Region: Alkene and Carbonyl Stretching

1.2K
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...
1.2K
IR Frequency Region: Alkyne and Nitrile Stretching01:22

IR Frequency Region: Alkyne and Nitrile Stretching

1.4K
Both alkyne (C≡C) and nitrile (C≡N) functional groups contain triple bonds and show stretching absorptions around the wavenumber range of 2100 to 2300 cm−1 in the diagnostic region of the IR spectra.
Comparing the stretching vibrational frequency of  C≡C triple bonds with that of double and single bonds, it is evident that C≡C triple bonds exhibit a higher stretching frequency than C=C double and C–C single bonds. Similarly, the C≡N triple bond...
1.4K

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Author Spotlight: Development and Application of SERS Flexible Substrates Using Synthesized AgNPs
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Empirical S=O stretch vibrational frequency map.

Kwang-Im Oh1, Carlos R Baiz1

  • 1Department of Chemistry, University of Texas at Austin, Austin, Texas 78705, USA.

The Journal of Chemical Physics
|December 23, 2019
PubMed
Summary
This summary is machine-generated.

Researchers developed a spectroscopic map for dimethyl sulfoxide (DMSO) in water. This tool interprets infrared spectra, quantifying hydrogen bonds and their lifetimes in DMSO-water mixtures.

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Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Computational Chemistry

Background:

  • Dimethyl sulfoxide (DMSO) water mixtures exhibit concentration-dependent bulk properties.
  • Understanding intermolecular interactions in these mixtures is crucial for various applications.
  • Spectroscopic methods are key to probing molecular behavior in liquid solutions.

Purpose of the Study:

  • To develop an empirical spectroscopic map for the sulfinyl (S=O) stretching mode of DMSO.
  • To enable interpretation of infrared (IR) absorption and 2D IR spectra.
  • To quantify hydrogen bond populations and lifetimes in DMSO-water mixtures.

Main Methods:

  • Development of an electrostatic map for the S=O stretching mode.
  • Parameterization against experimental IR absorption spectra of dilute DMSO in water.
  • Validation using molecular dynamics simulations and comparison with experimental 2D IR spectra.

Main Results:

  • The spectroscopic map accurately reproduces experimental S=O stretching frequencies across the DMSO concentration range.
  • The map captures the observed red-shift of approximately 10 cm-1 per hydrogen bond.
  • Simulated 2D IR spectra, generated using the map, align well with experimental data.

Conclusions:

  • The empirical frequency map provides a quantitative link between spectroscopic measurements and molecular dynamics.
  • This tool facilitates the investigation of intermolecular interactions and microscopic heterogeneity in DMSO-water mixtures.
  • The developed map is valuable for analyzing ultrafast dynamics in complex liquid systems.