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Updated: Jun 17, 2026

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
Published on: May 27, 2018
How the shape of an H-bonded network controls proton-coupled water activation in HONO formation
Rachael A Relph1, Timothy L Guasco, Ben M Elliott
1Department of Chemistry, Yale University, Post Office Box 208107, New Haven, CT 06520, USA.
Abstract:
Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)-bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.
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