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The molecular ion peak of a molecule in the mass spectrum provides vital information for molecular identification. However, conventional electron impact ionization can lead to the rapid dissociation of some molecular ions before they reach the detector. A milder ionization method is required to increase the lifetime of such ionized analyte molecules. Chemical ionization (CI) is a gas-phase protonation reaction useful for mass-analyzing analyte molecules that are easily protonated to yield the...
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The amount of energy required to remove the most loosely bound electron from a gaseous atom in its ground state is called its first ionization energy (IE1). The first ionization energy for an element, X, is the energy required to form a cation with 1+ charge:
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Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
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Published on: July 27, 2018

Electron ionisation of sulfur dioxide.

James D Fletcher1, Michael A Parkes, Stephen D Price

  • 1Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.

The Journal of Chemical Physics
|May 17, 2013
PubMed
Summary

This study measured ion yields from electron-sulfur dioxide (SO2) collisions, quantifying fragment ions and estimating the triple ionization potential of SO2 for the first time.

Area of Science:

  • Atomic and Molecular Physics
  • Chemical Physics
  • Mass Spectrometry

Background:

  • Electron ionization of molecules produces fragment ions, crucial for understanding molecular structure and dynamics.
  • Sulfur dioxide (SO2) is a significant atmospheric pollutant, and its ionization processes are key to atmospheric chemistry.
  • Quantifying partial ionization cross sections provides detailed insights into fragmentation pathways.

Purpose of the Study:

  • To measure relative precursor-specific partial ionization cross sections for fragment ions of sulfur dioxide (SO2).
  • To quantify ion yields for O(2+), O(+), SO(2+), S(+), O2(+), and SO(+) relative to SO2(+).
  • To experimentally estimate the triple ionization potential of SO2.

Main Methods:

  • Time-of-flight mass spectrometry coupled with two-dimensional ion coincidence detection.

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  • Electron ionization of SO2 over an energy range of 30 to 200 eV.
  • Computational chemistry methods to determine ionization potentials.

    • Main Results:

    • Relative partial ionization cross sections for various fragment ions were measured for the first time.
    • The formation of O(2+) following electron-SO2 collisions was quantified for the first time.
    • An experimental estimate of the triple ionization potential of SO2 was determined as 69.0 ± 3.6 eV.
    • A stepwise pathway for S(+) + 2O(+) formation was identified, occurring below the direct triple ionization energy.

    Conclusions:

    • The study provides the first detailed quantification of fragment ion yields from electron-impact ionization of SO2.
    • The experimental triple ionization potential of SO2 aligns well with computational predictions.
    • A novel stepwise mechanism contributes to the formation of specific fragment ions, bypassing direct trication formation.