Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules

Understanding the nature of H-bonding interactions is essential to modern sciences, such as biology, chemistry, and physics. Using density functional theory calculations, herein, we have identified two unique types existing in a single sheet mixed water–hydroxyl phase on close-packed metal surfaces, sharp contrast conventional H-bonds liquid water ices. Interestingly, shallow show reduced electrostatic Pauli repulsion interactions, with an polar character resulted from complete σ resonances, whereas deep exhibit enhanced dipolar feature originated hybrid orbital interactions. A trade-off-like cooperativity law was discovered, that is, strengthening internal bonds (dO–H) leads weakening external (dO:H) or vice versa. However, non-linear cooperativity, linear cooperativity. We also oxygen backbone rule adsorbate–metal has net effect analogy reducing O–O within adlayer. Furthermore, discovered several universality classes geometrical, vibrational, electronic spaces for types. Although shared by classes, contrasting are featured divergent trends significant overlapping, where competitive variations strengths basic rules cooperative The knowledge unconventional expands our current understanding ices points importance manipulation at levels. These findings not only shed new light probing fundamental general but insightful implications resolving interfacial water, ices, aqueous solutions.