Adsorbate Resonance-Assisted Hydrogen Bonding across Solid Interfaces

In this work, we identify and characterize a cooperative interaction between adsorbates in which hydrogen bonding and surface-mediated bond redistribution reinforce one another across a solid interface. We show that this phenomenon, which we term adsorbate resonance-assisted hydrogen bonding (ARAHB), arises from the transfer of covalent bond character along a hydrogen-bond coordinate, coupled to bond redistribution throughout the adsorbate-surface complex. We develop a computational workflow to test and identify ARAHB among coadsorbates. Although first identified computationally, we connect ARAHB to previous experimental observations of symmetric hydrogen-bonded water/hydroxyl surface structures. Through computational screening of homo-and heteronuclear adsorbate dimers, we identify ARAHB across a range of X − H · · · Y motifs (X, Y = N, O, F). These interactions are characterized by strong adsorbate-adsorbate stabilization, substantial redistribution of surface bonding, and pronounced X − H bond elongation, demonstrating the generality of the phenomenon. We find a strong correlation between interaction energetics and geometry, culminating in nearly equalized X − H · · · Y configurations that exhibit the strongest stabilization. We find that the donor species principally determines the interaction geometry, whereas the acceptor largely governs the extent of bond redistribution. The overall stabilization reflects contributions from both species as well as the local adsorption environment. These findings establish ARAHB as a general interaction mechanism at solid interfaces and provide a framework for understanding cooperative adsorbate interactions that cannot be inferred by isolated adsorbate behavior.