Resonant Inelastic X-Ray Scattering Reveals Hidden Local Transitions of the Aqueous OH Radical

Physical review letters 124(23), 236001 (2020). doi:10.1103/PhysRevLett.124.236001
Resonant inelastic x-ray scattering (RIXS) provides remarkable opportunities to interrogate ultrafast dynamics in liquids. Here we use RIXS to study the fundamentally and practically important hydroxyl radical in liquid water, OH($aq$). Impulsive ionization of pure liquid water produced a short-lived population of OH($aq$), which was probed using femtosecond x-rays from an x-ray free-electron laser. We find that RIXS reveals localized electronic transitions that are masked in the ultraviolet absorption spectrum by strong charge-transfer transitions—thus providing a means to investigate the evolving electronic structure and reactivity of the hydroxyl radical in aqueous and heterogeneous environments. First-principles calculations provide interpretation of the main spectral features.
Published by APS, College Park, Md.