Kinetics of small ion evaporation from the charge and mass distribution of multiply charged clusters in electrosprays.

The distribution of charge z and radii R in clusters electrosprayed from formamide solutions of tetraheptylammonium bromide was investigated by selecting those within a narrow range of electrical mobilities Z(1) in a first differential mobility analyzer (DMA), reducing their charge to unity by passage through a neutralizing chamber containing a radioactive (alpha) source, and measuring the mobilities Z(z) of the resulting discrete set of singly charged clusters in a second DMA. After correcting for the polarization contribution to cluster drag, the tandem DMA data yield the range of radii present at detectable levels for each charge state up to z = 9. Because small ion evaporation from electrospray drops leads to charge loss when a drop reaches a certain critical radius R(crit)(z), the measured maximum and minimum cluster radii associated with a given z can be used to infer the activation energy Delta for ion evaporation as a function of drop charge and curvature. These results confirm the Iribarne-Thomson ion-evaporation mechanism, and support earlier theoretical expressions for the functional form of Delta(z,R). The different phenomenon of ion evaporation from metastable multiply charged dry clusters is also observed at characteristic times of 1 s. Its activation energy is estimated as approximately 0.3 eV larger than for ion evaporation from the drops. This new process complicates the interpretation of the present measurements in terms of ion evaporation from liquid surfaces, but introduces no radical change in the picture. It helps understand why salt clusters with more than two or three charges are harder to see in mass spectrometers than in mobility studies under ambient conditions. Copyright 2000 John Wiley & Sons, Ltd.