Abstract
Clusters formed in positive electrosprays of several room-temperature molten salts A+B- dissolved (∼1 mM) in acetonitrile are investigated in their natural charge state by high resolution differential mobility analysis. They exhibit a peculiar pattern of singly and doubly charged cluster ions (A+)z(AB)n. For z = 1, there is a first series of clusters with n values typically from 0 to 3, peaking at about n = 1, and a second series with n values up to 8−12, peaking at about n = 6. Doubly charged clusters exhibit also two well-separated groups of ions. The two distinct series observed are attributed to two different ionization mechanisms, the small clusters forming by ion evaporation, and the large ones as charged residues from evaporating drops. The new ability to distinguish ions formed by either scheme provides information on the ranges of cluster sizes that may ion evaporate. Noteworthy is the observation that clusters grouping two cations do evaporate directly from the liquid surface.
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