Time-Resolved Photoelectron Imaging of Acetone with 9.3 eV Photoexcitation.

Ultrafast electronic relaxation following 9.3 eV photoexcitation of gaseous acetone was investigated with time-resolved photoelectron imaging spectroscopy. An intense photoionization signal due to a transition from the 41A1(π,π*) state to the D1(π-1) cationic state diminishes within 50 fs, owing to vibrational wave packet motion leaving our observation energy window. Additional photoionization signals were assigned to transitions from Rydberg states with principal quantum numbers of 3-8 to the D0(n-1) cationic state, created by strong vibronic couplings with the bright 41A1(π,π*) state. The deactivation processes of the 41A1(π,π*) and Rydberg states are discussed based on their decay profiles obtained from a time-energy map of photoelectron kinetic energy distributions.