Orientational Water Bonding on Pt(111): Beyond the Frontier Orbital Principle.

For decades, our understanding of water-metal bonding has been dominated by the frontier orbital principle in which globally stable water-metal interactions are ruled by HOMO interacting with metal surfaces. Using density functional theory calculations, herein, we have revealed that the frontier orbital principle cannot be applied to metastable water bonding on Pt(111), where the decisive role of HOMO is replaced by HOMO-1 in terms of the greatest orbital shifts and depopulations as the two different bonding indicators. Unlike the stable water configuration in which both HOMO-1 and HOMO prefer to overlap with metal states through σ-like orbital interactions, metastable configurations exhibit delicate competition or balance between σ-like and π-like orbital interactions exerted by HOMO-1 and HOMO, respectively. These findings have significantly deepened our understanding of orbital roles in water-metal bonding interactions and bridged the gap between theoretical understanding of electrified waters at electrochemical interfaces and water science on metal surfaces.