Hydrogen-Bond Topology is More Important than Acid/Base Strength in Atmospheric Prenucleation Clusters
Harold, S.E.; Bready, C.J.; Juechter, L.A.; Kurfman, L.A.; Vanovac, S.; Fowler, V.R.; Mazaleski, G.E.; Odbadrakh, T.T.; Shields, G.C. “Hydrogen-Bond Topology is More Important than Acid/Base Strength in Atmospheric Prenucleation Clusters.” J. Phys. Chem. A 2022, 126, 10, 1718-1728.
We explored the hypothesis that on the nanoscale level, acids and bases might exhibit different behavior than in bulk solution. Our study system consisted of sulfuric acid, formic acid, ammonia, and water. We calculated highly accurate Domain-based Local pair-Natural Orbital- Coupled-Cluster/Complete Basis Set (DLPNO-CCSD(T)/CBS) energies on DFT geometries and used the resulting Gibbs free energies for cluster formation to compute the overall equilibrium constants for every possible cluster. The equilibrium constants combined with the initial monomer concentrations were used to predict the formation of clusters at the top and the bottom of the troposphere. Our results show that formic acid is as effective as ammonia at forming clusters with sulfuric acid and water. The structure of formic acid is uniquely suited to form hydrogen bonds with sulfuric acid. Additionally, it can partner with water to form bridges from one side of sulfuric acid to the other, hence demonstrating that hydrogen bonding topology is more important than acid/base strength in these atmospheric prenucleation clusters.
Journal of Physical Chemistry A