Hydrogen-atom roaming reactions in water clusters: Unveiling an unusual dimension of water reactivity through first-principles calculations and machine learning

Abstract

Water mediates a broad range of chemical reactions, including proton transfer, bond rearrangement, and conventional radical processes, defining a continuously expanding repertoire of intrinsic reactivity. However, roaming, a fundamental reaction mechanism that a departing fragment bypasses the minimum energy path to recombine, has not been identified in water itself. Here, we report the discovery of hydrogen-atom roaming reactions in water clusters through high-precision ab initio calculations of first-principles. A neutral hydrogen atom departs as a radical, roams across the flat potential energy surface, and recombines along pathways that connect the same reactants and products as known hydrogen-bond network rearrangements. Interpretable machine learning analysis identifies the reactant dipole moment as the decisive switch governing whether roaming occurs, underpinned by exchange-repulsion and electrostatic interactions. Once roaming is initiated, polarizability and spin population determine barrier heights, while the charge distribution of the roaming hydrogen atom governs barrier widths, collectively shaped by electrostatic, orbital, and dispersion contributions. These findings establish hydrogen-atom roaming as a previously unrecognized intrinsic reaction class in water, complementing a fundamental dimension to the mechanistic picture of water reactivity.