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UV–Vis Spectroscopy: Beer–Lambert Law01:09

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The Beer-Lambert law describes the relationship between absorbance and concentration, which combines the principles established by scientists Johann Heinrich Lambert and August Beer. Lambert's law states that when light passes through a medium, the loss in intensity is directly proportional to the original intensity and the path length of the light. Beer's law proposed that the transmittance of a solution remains constant if the product of concentration and path length is constant. The...
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IR Spectroscopy: Molecular Vibration Overview01:24

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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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IR and UV–Vis Spectroscopy of Aldehydes and Ketones01:29

IR and UV–Vis Spectroscopy of Aldehydes and Ketones

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Infrared spectroscopy, also known as vibrational spectroscopy, is mainly used to determine the types of bonds and functional groups in molecules. In aldehydes and ketones, the carbonyl (C=O) bond shows an absorption around 1710 cm-1. The C=O bond vibration of an aldehyde occurs at lower frequencies than that of a ketone. In addition to the C=O absorption in an aldehyde, the aldehydic C–H bond also gives two peaks in the 2700–2800 cm-1 range. This absorption, coupled with the...
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Mass Spectrometry: Alcohol Fragmentation01:03

Mass Spectrometry: Alcohol Fragmentation

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Alcohols (R-OH) ionize to lose one non-bonded electron from the oxygen atom, forming molecular ions. Due to their tendency to fragment rapidly, the intensity of the molecular ion peak in the mass spectrum is weak or sometimes absent. The fragmentation patterns for alcohols occur in two ways, i.e. ⍺-cleavage and dehydration. During ⍺-cleavage, the bond at the ⍺-position adjacent to the hydroxyl group cleaves to give a resonance-stabilized cation and a radical. However,...
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UV–Vis Spectrometers01:14

UV–Vis Spectrometers

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The absorbance of UV and visible (UV–visible) radiations is measured using a UV–visible spectrophotometer. Deuterium lamps, which emit UV radiation, and tungsten lamps, which produce radiation in the visible region, are used as light sources in UV–visible spectrophotometers. A monochromator or prism is used for diffraction grating, i.e., to split the incoming radiation into different wavelengths. A system of slits is used to focus the desired wavelength on the sample cell.
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IR Spectrum Peak Broadening: Hydrogen Bonding01:23

IR Spectrum Peak Broadening: Hydrogen Bonding

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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...
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Related Experiment Video

Updated: Jul 8, 2025

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
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Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy

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Quantifying the Nearly Random Microheterogeneity of Aqueous tert-Butyl Alcohol Solutions Using Vibrational

Andres S Urbina1, Lyudmila V Slipchenko1, Dor Ben-Amotz1

  • 1Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.

The Journal of Physical Chemistry Letters
|December 11, 2023
PubMed
Summary

Aqueous tert-butyl alcohol (TBA) solutions exhibit microheterogeneous structures. This study quantifies TBA aggregation using Raman-MCR, QM/EFP, and MD simulations, revealing insights into self-assembly.

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Area of Science:

  • Physical Chemistry
  • Solution Chemistry
  • Computational Chemistry

Background:

  • Aqueous solutions of tert-butyl alcohol (TBA) exhibit complex microheterogeneous structures.
  • Understanding these structures is crucial for various chemical and biological processes.

Purpose of the Study:

  • To quantify the microheterogeneous structure of aqueous TBA solutions.
  • To compare experimental findings with various simulation and theoretical predictions.

Main Methods:

  • Experimental Raman multivariate curve resolution (Raman-MCR) C-H frequency shift measurements.
  • Combined quantum mechanical and effective fragment potential (QM/EFP) calculations.
  • Molecular dynamics (MD) simulations using CHARMM generalized force field (CGenFF) and OPLS-AA force fields.
  • Random mixture (RM) and finite lattice (FL) predictions.

Main Results:

  • Microheterogeneous aggregation in aqueous TBA solutions is slightly less than MD predictions (CGenFF, OPLS-AA).
  • Aggregation is slightly more than random mixture (RM) predictions.
  • Onset of microheterogeneity occurs when solute contact free energies are significantly smaller than thermal fluctuations.

Conclusions:

  • The study provides a quantitative assessment of microheterogeneity in aqueous TBA solutions.
  • Findings suggest a fundamental bound for the onset of microheterogeneity relevant to biological self-assembly.