Dissociation dynamics: Measurements of decay fractions of metastable ammonia cluster ions

The decay fractions of metastable ammonia cluster ions which undergo unimolecular (evaporative) dissociation in a time window of 1–40 μs were measured by using a reflection time-of-flight mass spectrometer. Corrections concerning instrumental artifacts and ion trajectory of parents and daughters are made to imporve the precision of the measurements. The data are used to derive the Gspann parameter and heat capacity of clusters as described in evaporative ensemble model of metastable dissociation. Using the dissociation fractions measured in the present studies, in conjunction with kinetic energy release values previously measured in our laboratory, we apply Klots’ evaporative ensemble model to obtain binding energies of ammonia cluster ions (NH3)nH+, 4≤n≤17. The deduced binding energy values are found to be in very good agreement with both thermochemical data and Engelking’s modified statistical theory.