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Related Concept Videos

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...
Mass Spectrometry: Alkene Fragmentation00:59

Mass Spectrometry: Alkene Fragmentation

Alkenes lose one electron from the unsaturated π bond upon ionization and form stable molecular ions. Further fragmentation of alkenes occurs through three different reaction pathways. The most prominent fragmentation is the cleavage at the allylic position. The resultant allylic carbocation is resonance stabilized. In the mass spectra of terminal alkenes, this fragment appears at a mass-to-charge ratio of 41. In the internal alkenes, where there are two choices of allylic cleavage, the...
Mass Spectrum01:23

Mass Spectrum

A mass spectrum is the graphical representation of the relative abundance of the charged fragments in an analyte plotted against their mass-to-charge ratio (m/z). The plot's x-axis represents the ratio of the mass of the charged fragment to the number of charges it carries. The y axis of the plot represents the relative abundance of each charged species. The relative abundance is calculated from the signal intensity of each charged species recorded at the detector. The most intense signal (the...
Mass Spectrometry: Long-Chain Alkane Fragmentation01:18

Mass Spectrometry: Long-Chain Alkane Fragmentation

The molecular ions of linear alkanes prefer to fragment at the carbon-carbon bond away from the end of the chain since the cleavage of an inner bond creates a stable carbocation and a stable radical. Consequently, the mass signals of linear alkanes feature intense peaks in the middle of the mass-to-charge ratio plot with weaker peaks on either end. The fragmentation of each carbon-carbon bond with the release of a methyl group in each splitting leads to prominent peaks in the mass spectra...
Mass Spectrometry: Branched Alkane Fragmentation01:29

Mass Spectrometry: Branched Alkane Fragmentation

This lesson delves into the mass spectrometry of branched alkane fragmentation. Branched alkanes possess secondary or tertiary carbon atoms, which generate relatively stable carbocations if the cleavage occurs at the branching point. The high stability of carbocations drives the instant fragmentation of branched alkanes. Accordingly, the branched alkane's molecular ion peak is very weak or invisible in the mass spectra, especially in comparison to a linear alkane.
Inductive Effects on Chemical Shift: Overview01:27

Inductive Effects on Chemical Shift: Overview

The protons in unsubstituted alkanes are strongly shielded with chemical shifts below 1.8 ppm. Methine, methylene, and methyl protons appear at approximately 1.7, 1.2 and 0.7 ppm, while the proton signal from methane appears at 0.23 ppm. An electronegative substituent, such as chlorine, withdraws the electron density from the protons, increasing their chemical shift. Progressive substitution of the hydrogens in methane by chlorine shifts the proton signals increasingly downfield, to 3.05 ppm in...

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Stimulated Stokes and Antistokes Raman Scattering in Microspherical Whispering Gallery Mode Resonators
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Multimode resonant Auger scattering from the ethene molecule.

Ji-Cai Liu1, Christophe Nicolas, Yu-Ping Sun

  • 1Theoretical Chemistry, School of Biotechnology, Royal Institute of Technology, S-106 91 Stockholm, Sweden.

The Journal of Physical Chemistry. B
|March 5, 2011
PubMed
Summary

Resonant Auger spectroscopy of ethene reveals distinct spectral features. Multimode calculations explain vibrational distributions and energy evolution in these electron spectra.

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Area of Science:

  • Molecular Spectroscopy
  • Quantum Chemistry
  • X-ray Photoelectron Spectroscopy

Background:

  • Resonant Auger spectroscopy provides insights into electronic states of molecules.
  • Vibrational resolution is crucial for detailed analysis of molecular dynamics.
  • The C1s(-1)1b(2g)(π*) resonance in ethene is a key area for studying electron dynamics.

Purpose of the Study:

  • To measure and interpret resonant Auger spectra of ethene with vibrational resolution.
  • To assign spectral features using ab initio multimode calculations.
  • To understand the evolution of spectral features with excitation energy.

Main Methods:

  • Experimental measurement of resonant Auger spectra of ethene.
  • Vibrational resolution analysis of spectral data.
  • Ab initio multimode quantum chemical calculations.

Main Results:

  • Assignment of main features in the resonant Auger spectra.
  • Explanation of extended vibrational distributions by multimode excitation.
  • Observation of two distinct spectral features following Raman and non-Raman dispersion laws.
  • Correlation of non-Raman band formation thresholds with X-ray absorption spectrum structure.

Conclusions:

  • Ab initio multimode calculations accurately interpret experimental resonant Auger spectra of ethene.
  • Multimode excitation during scattering explains spectral evolution.
  • The "double-edge" structure in X-ray absorption spectra influences non-Raman band formation.