IR Photochemistry in an Electronically Excited State

Abstract

Induced by an intense infrared laser field, fragmentation of a polyatomic molecule in its electronic ground state requires the absorption of many photons. The high vibrational energy necessary to drive a molecule to the dissociation limit might play a key role in preventing intramolecularly selective photochemistry. At high vibrational energy the density of background states is large and the oscillator strength of the pumped mode spreads over a large number of vibrational states. Thus, the initially localized energy is rapidly distributed over the vibrational degrees of freedom.