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Related Concept Videos

IR Spectrum Peak Broadening: Hydrogen Bonding01:23

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 hydrogen bonding...
UV–Vis Spectroscopy of Conjugated Systems01:32

UV–Vis Spectroscopy of Conjugated Systems

Organic compounds with conjugated double bonds show strong absorption features in the UV–visible region of the electromagnetic spectrum attributed to π → π* electronic excitations. Generally, a UV–vis absorption spectrum is recorded as a plot of absorbance vs wavelength. The wavelength of maximum absorbance, which manifests as a peak in the absorption spectrum, is denoted as λmax.
One of the factors influencing λmax is the extent of conjugation in the...
UV–Vis Spectroscopy: Molecular Electronic Transitions01:16

UV–Vis Spectroscopy: Molecular Electronic Transitions

In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this process,...
IR Spectroscopy: Molecular Vibration Overview01:24

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 Vibration01:16

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...
Atomic Absorption Spectroscopy: Interference01:25

Atomic Absorption Spectroscopy: Interference

Interference leads to systematic error in atomic absorption (AA) measurements by enhancing or diminishing the analytical signal or the background. These interferences can be grouped into three main categories: spectral interference, chemical interference, and physical interference.
Spectral interference occurs when signals from other elements or molecules overlap with the analyte signal, falsely elevating or masking the analyte's absorbance. This interference can be corrected using Zeeman,...

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Updated: May 23, 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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Deconstructing water's diffuse OH stretching vibrational spectrum with cold clusters.

Nan Yang1, Chinh H Duong1, Patrick J Kelleher1

  • 1Sterling Chemistry Laboratory, Yale University, New Haven, CT 06520, USA.

Science (New York, N.Y.)
|April 20, 2019
PubMed
Summary
This summary is machine-generated.

Investigating water molecules in a Cs+·(D2O)20 ion cage reveals how hydrogen-bond structures influence their spectral signatures. This study details the site-dependent correlations between hydroxy group (OH) frequencies and anharmonic contributions.

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Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Materials Science

Background:

  • Water's diffuse vibrational spectrum hinders understanding of hydrogen-bond effects on individual hydroxy group (OH) oscillators.
  • Characterizing water's hydrogen-bond network is crucial for many chemical and biological processes.

Purpose of the Study:

  • To spectrally identify individual water molecules within a defined hydrogen-bond environment.
  • To correlate specific hydrogen-bond topologies with the vibrational frequencies of OH oscillators.
  • To quantify anharmonic contributions to water's vibrational spectrum.

Main Methods:

  • Utilizing cold, isotopically labeled water cluster ions (H2O and D2O).
  • Embedding single H2O molecules in Cs+·(D2O)20 clathrate-like cage structures.
  • Analyzing infrared (IR) spectral signatures to probe OH group vibrations.

Main Results:

  • Observed distinct spectral signatures for water molecules at different sites within the cage.
  • Established site-dependent correlations between the frequencies of the two OH groups on a single water molecule.
  • Identified the bound OH group as responsible for lower-energy spectral bands.
  • Revealed homogeneous linewidths and quantified anharmonic coupling to intramolecular bending and intermolecular modes.

Conclusions:

  • The study provides direct spectral evidence of how hydrogen-bond topology influences individual water molecule vibrations.
  • Site-specific analysis allows for detailed understanding of spectral contributions from different OH oscillators.
  • Quantification of anharmonic effects offers insights into vibrational energy flow in water clusters.