Hydration motifs of ammonium bisulfate clusters show complex temperature dependence

The role of water in the formation of particles from atmospheric trace gases is not well understood, in large part due to difficulties in detecting its presence under atmospheric conditions and the variety of possible structures that must be screened computationally. Here, we use infrared spectroscopy and variable-temperature ion trap mass spectrometry to investigate the structural motifs adopted by water bound to ammonium bisulfate clusters and their temperature dependence. For clusters featuring only acid-base linkages, water adopts a bridging arrangement spanning an adjacent ammonium and bisulfate. For larger clusters, water can also insert into a bisulfate-bisulfate hydrogen bond, yielding hydration isomers with very similar binding energies. The population of these isomers shows a complex temperature evolution, as an apparent third isomer appears with a temperature dependence that is difficult to explain using simple thermodynamic arguments. These observations suggest that the thermodynamics of water binding to atmospheric clusters such as these may not be straightforward.