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Related Experiment Videos

Ammoniated electron as a solvent stabilized multimer radical anion.

Ilya A Shkrob1

  • 1Chemistry Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, USA. shkrob@anl.gov

The Journal of Physical Chemistry. A
|March 17, 2006
PubMed
Summary

Excess electrons in liquid ammonia form solvent-stabilized anions, not just cavity electrons. This new model explains NMR and IR spectroscopy data, suggesting similar mechanisms in other solvents.

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Area of Science:

  • Physical Chemistry
  • Theoretical Chemistry

Background:

  • The ammoniated electron is traditionally modeled as a cavity electron.
  • This model suggests the electron's wave function occupies a void within ammonia molecules.

Purpose of the Study:

  • To investigate an alternative model for the ammoniated electron.
  • To explore the ammoniated electron as a solvent-stabilized multimer radical anion.

Main Methods:

  • Density functional theory (DFT) calculations.
  • Analysis of nuclear magnetic resonance (NMR) spectroscopy data (Knight shifts).
  • Analysis of infrared (IR) spectroscopy data (vibrational modes).

Main Results:

  • The multimer radical anion model semiquantitatively explains observed Knight shifts for 1H and 14N nuclei.

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  • The model accounts for the downshifted stretching and bending modes in IR spectroscopy.
  • The cavity formation is attributed to repulsion between negatively charged solvent molecules.

    • Conclusions:

    • The ammoniated electron can be described as a solvent-stabilized multimer radical anion.
    • This model provides a better fit for spectroscopic observations than the cavity electron model.
    • Similar electron stabilization mechanisms may occur in other aprotic solvents.