Time-resolved photoelectron spectroscopy of Fe(CO)(5) multiple fragmentation: theoretical considerations

We regard dissociation processes induced by femtosecond excitation of iron pentacarbonyl. In common time-resolved ionization experiments, the total io n yield is detected as a function of the delay time between pump- and probe -pulse. If several ionic fragments are produced, these measurements cannot distinguish between charged molecules produced via ionization of neutral mo lecules or fragmentation of larger molecular ions. We show that time-resolv ed photoelectron spectroscopy does not suffer from this deficiency and thus provides a unique tool to investigate neutral fragmentation processes. (C) 2001 Elsevier Science B.V. All rights reserved.