Vibrational Autodetachment-Intramolecular Vibrational Relaxation Translated into Electronic Motion

If a negative ion has vibrational energy in excess of the binding energy of its most weakly bound electron, the anion call 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 oil the intramolecular vibrational relaxation processes that take place between excitation and electron emission. We present examples oil how vibrational autodetachment call be used to obtain infrared spectra of molecular anions, and we discuss how a vibrational autodetachment photoelectron spectrum call be modeled, using vibrational autodetachment after excitation of CH stretching modes of nitromethane anions as a case study.