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Related Concept Videos

Infrared (IR) Spectroscopy: Overview01:09

Infrared (IR) Spectroscopy: Overview

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When electromagnetic radiation passes through a material, atoms or molecules transition from a lower to a higher energy state by absorbing radiation corresponding to the energy difference between the two states. The absorption of infrared (IR) radiation causes transitions between vibrational energy levels in a molecule. Therefore, IR spectroscopy is a useful analytical tool for determining the molecular structure of molecules.
Different compounds display unique properties due to their...
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IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration01:16

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration

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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...
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IR Spectrum01:19

IR Spectrum

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When infrared (IR) radiation passes through a molecule, the bonds stretch or bend by absorbing the radiation. This absorption creates the molecule's absorption spectrum, which is the plot of its percentage transmittance versus wavenumber.
Transmittance is defined as the ratio of the radiant power passing through a sample to that from the radiation's source. Multiplying the transmittance by 100 gives the percent transmittance (%T), which varies between 100% (no absorption) and 0%...
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IR Frequency Region: Fingerprint Region01:03

IR Frequency Region: Fingerprint Region

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IR spectra are divided into two main regions: the diagnostic region and the fingerprint region. The diagnostic region of the spectrum lies above 1500 cm−1. The absorptions resulting from single-bond vibrations of the N–H, C–H, and O–H stretch at higher wavenumbers and appear on the left side of the spectrum. The stretching absorptions of the C≡C and C≡N occur between 2100–2300 cm−1. In contrast, those arising from stretching absorptions of the...
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IR Spectrum Peak Intensity: Amount of IR-Active Bonds00:55

IR Spectrum Peak Intensity: Amount of IR-Active Bonds

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When infrared radiation is passed through a molecule, absorption occurs if the molecule's vibration leads to a substantial change in its bond dipole moment. Transitions between vibrational energy levels, typically corresponding to infrared frequencies (4000–400 cm−1), allow absorption if the vibration significantly alters the dipole moment, making the molecule infrared active. The molecular bonds have different stretching and bending vibrations, resulting in various peaks with...
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IR Spectroscopy: Molecular Vibration Overview01:24

IR Spectroscopy: Molecular Vibration Overview

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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...
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Updated: Sep 16, 2025

In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework
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Solvent Exclusion Effect on Infrared Absorption Spectroscopy.

Young Jong Lee1, Seong-Min Kim1, Sang Hak Lee1,2

  • 1Biosystems and Biomaterials Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States.

Analytical Chemistry
|July 9, 2025
PubMed
Summary
This summary is machine-generated.

Accurate absorption spectroscopy requires correcting for the solvent exclusion effect, where solvent molecules are displaced by solute molecules. This study introduces a simple volumetric method using partial specific volume (PSV) to retrieve accurate solute-only spectra, crucial for molecular analysis.

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Area of Science:

  • Spectroscopy
  • Analytical Chemistry
  • Biophysics

Background:

  • Absorption spectroscopy relies on solvent transmission as a reference, assuming no solvent light absorption.
  • Solvent exclusion (SE) effect lowers absorbance, causing errors, especially with water's strong absorption peaks.
  • Current methods for SE correction are limited by spectral breadth and laser source capabilities.

Purpose of the Study:

  • To develop a simple volumetric method for correcting the solvent exclusion effect in absorption spectroscopy.
  • To accurately retrieve solute-only absorption spectra, particularly for proteins in aqueous solutions.
  • To validate the method's effectiveness for both globular and small-molecule solutes.

Main Methods:

  • A volumetric solvent exclusion (SE) correction method utilizing partial specific volume (PSV) was developed.
  • Spectra were acquired using a quantum cascade laser (QCL) spectroscopy system with solvent absorption compensation (SAC).
  • The method was tested on globular proteins and small-molecule solutes in aqueous solutions.

Main Results:

  • The PSV-based SE correction method successfully retrieved accurate solute-only absorption spectra.
  • The method demonstrated effectiveness for globular proteins and small-molecule solutes.
  • High molecular sensitivity was achieved with the QCL-SAC system and SE correction.

Conclusions:

  • The simplified PSV-based SE correction is a robust method for accurate quantitation in absorption spectroscopy.
  • This technique overcomes limitations of existing methods, especially near strong solvent absorption bands.
  • The approach enhances the reliability of spectroscopic analysis for diverse solutes in solution.