Establishing the structural motifs present in small ammonium and aminium bisulfate clusters of relevance to atmospheric new particle formation

Atmospheric new particle formation is the process by which atmospheric trace gases, typically acids and bases, cluster and grow into potentially climatically relevant particles. Here, we evaluate the structures and structural motifs present in small cationic ammonium and aminium bisulfate clusters that have been studied both experimentally and computationally as seeds for new particles. For several previously studied clusters, multiple different minimum-energy structures have been predicted. Vibrational spectra of mass-selected clusters and quantum chemical calculations allow us to assign the minimum-energy structure for the smallest cationic cluster of two ammonium ions and one bisulfate ion to a C_S-symmetry structure that is persistent under amine substitution. We derive phenomenological vibrational frequency scaling factors for key bisulfate vibrations to aid in the comparison of experimental and computed spectra of larger clusters. Finally, we identify a previously unassigned spectral marker for intermolecular bisulfate–bisulfate hydrogen bonds and show that it is present in a class of structures that are all lower in energy than any previously reported structure. Tracking this marker suggests that this motif is prominent in larger clusters as well as ∼180 nm ammonium bisulfate particles. Taken together, these results establish a set of structural motifs responsible for binding of gases at the surface of growing clusters that fully explain the spectrum of large particles and provide benchmarks for efforts to improve structure predictions, which are critical for the accurate theoretical treatment of this process.