Femtosecond Multiphoton Ionization Research Articles

Formation and metastable decomposition of unprotonated ammonia cluster ions upon femtosecond ionization

The formation and metastable dissociation mechanism of unprotonated ammonia cluster ions, (NH3)+n, produced by multiphoton ionization (MPI) at 624 nm and a nominal pulse width of 350 fs, are investigated through a reflectron time-of-flight (TOF) mass spectrometric technique. Detection of the unprotonated ions after femtosecond and nanosecond multiphoton ionization under various intensity conditions is explained. The role of the energy of the ionizing photons, and the observation of these ions after femtosecond MPI is examined. The formation of the unprotonated series is found to be a function of intensity in the case of ionization on the nanosecond time scale, but not so for the femtosecond time domain. The results can be explained in terms of ionization mechanisms and ionizing pulse durations. The findings of the present study suggest that the unprotonated ions are trapped behind the barrier to intracluster proton transfer and/or concomitant NH2 loss. The studies of metastable decomposition also reveal that the unprotonated ammonia cluster ions dissociate in the field-free region of the TOF by losing an NH2 radical rather than via the evaporative loss of NH3 as occurs for protonated clusters. Additionally, isotopic investigations of the unimolecular decay reveal a strong dependence on the conditions of cluster formation. The cluster formation condition dependence of the unimolecular decay is further investigated by altering formation temperatures and observing the consequences reflected by changes in the spontaneous metastable decay rate constant. This is a unique example of a cluster system whose metastable dissociation does not obey an evaporative ensemble model.

A comparison of femtosecond and nanosecond multiphoton ionization and dissociation for some nitro‐molecules

AbstractResonance‐enhanced multiphoton ionization spectrometry (REMPI), using time‐of‐flight mass spectrometers and tuned lasers, has proved an important ultra‐sensitive analytical technique. Nevertheless, conventional nanosecond REMPI suffers from a number of shortcomings: most importantly, REMPI often fails through rapidly (pre)dissociating states. In the case of thermally labile molecules, which include the nitro‐molecules, either no or very small parent or high/mass fragment ion peaks exist, making the interpretation of the mass spectra ambiguous at best and often impossible. Femtosecond laser mass spectrometry (FLMS) can often ‘defeat’ these dissociative states, resulting in large parent or high‐mass fragment ion peaks which make the interpretation less ambiguous. In the present paper, nanosecond and femtosecond multiphoton ionization and fragmentation are compared using time‐of‐flight mass spectrometry for NO2 gas and a number of different nitro‐molecules: nitromethane, nitrobenzene, m‐nitrotoluene, dinitrotoluene and trinitrotoluene.