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Updated: Jun 15, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Vibrational autodetachment-intramolecular vibrational relaxation translated into electronic motion
C L Adams1, H Schneider, J M Weber
1JILA, NIST, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
Abstract:
If a negative ion has vibrational energy in excess of the binding energy of its most weakly bound electron, the anion can undergo vibrational autodetachment, similar to thermionic emission. When this effect occurs after targeted infrared excitation of a specific vibrational mode in the anion, it encodes information on the intramolecular vibrational relaxation processes that take place between excitation and electron emission. We present examples on how vibrational autodetachment can be used to obtain infrared spectra of molecular anions, and we discuss how a vibrational autodetachment photoelectron spectrum can be modeled, using vibrational autodetachment after excitation of CH stretching modes of nitromethane anions as a case study.
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