Formation of Eigen or Zundel Features at Protonated Water Cluster–Aromatic Interfaces

Abstract

AbstractInterfacial interactions of protonated water clusters adsorbed at aromatic surfaces play an important role in biology, and in atmospheric, chemical and materials sciences. Here, we investigate the interaction of protonated water clusters ((H+H2O)n (where n=1–3)) with benzene (Bz), coronene (Cor) and dodecabenzocoronene (Dbc)). To study the structure, stability and spectral features of these complexes, computations are done using DFT‐PBE0(+D3) and SAPT0 methods. These interactions are probed by AIM electron density topography and non‐covalent interactions index (NCI) analyses. We suggest that the excess proton plays a crucial role in the stability of these model interfaces through strong inductive effects and the formation of Eigen or Zundel features. Also, computations reveal that the extension of the π‐aromatic system and the increase of the number of water molecules in the H‐bounded water network led to a strengthening of the interactions between the corresponding aromatic compound and protonated water molecules, except when a Zundel ion is formed. The present findings may serve to understand in‐depth the role of proton localized at aqueous medium interacting with large aromatic surfaces such as graphene interacting with acidic liquid water. Besides, we give the IR and UV‐Vis spectra of these complexes, which may help for their identification in laboratory.