Vibrational autodetachment-intramolecular vibrational relaxation translated into electronic motion

C L Adams; H Schneider; J M Weber

doi:10.1021/jp910675n

Vibrational autodetachment-intramolecular vibrational relaxation translated into electronic motion

J Phys Chem A. 2010 Apr 1;114(12):4017-30. doi: 10.1021/jp910675n.

Authors

C L Adams¹, H Schneider, J M Weber

Affiliation

¹ JILA, NIST, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.

PMID: 20205435
DOI: 10.1021/jp910675n

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.