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

The radiolysis of liquid water and the radiation-matter interactions that happen in aqueous environments are important to the fields of chemistry, materials, and environmental sciences, as well as the biological and physiological response to extreme conditions and medical treatments. The initial stage of radiolysis is the ultrafast response, or hole dynamics, that triggers 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 dynamics study to provide a more complete description of the ultrafast dynamics and reactive events initiated by photoionization of water. After sudden ionization, a range of processes, including 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 is elucidated.