The "Hole" Story in Ionized Water from the Perspective of Ehrenfest Dynamics

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The radiolysis of liquid water and the radiation-matter interactions that happen in aqueous
environments are important to the elds of chemistry, materials, and environmental sciences, as well as biological and physiological response to extreme conditions and medical treatments. The initial stage of radiolysis is the ultrafast response, or hole dynamics, that trigger chemical processes within complex energetic landscapes that may include reactivity. A fundamental understanding necessitates the use of theoretical methods that are capable of simulating both ultrafast coherence and non-adiabatic energy transfer pathways. In this work, we carry out an ab initio Ehrenfest dynamic study in order to provide a more complete description of the ultrafast dynamics and reactive events initiated by photoionization of water. After sudden ionization, the range of processes that include hole trapping and transfer, large OH oscillations, proton transfer and subsequent relay, formation of the metastable Zundel complex, and long-lived coherence, are identified and new insight into their driving forces are elucidated.