How Alkali Metal Cations Affect the Structure and Reactivity of the Hydrated Dielectron

Hydrated electrons of opposite spins pair to form dielectrons at sufficiently high concentrations that can be achieved by dissolution of alkali metals in water. While experimental investigations of these systems are challenging due to their vigorous, even explosive, reactivity, simulations open the possibility to characterize the structure and reactivity of hydrated dielectrons and the effects of alkali cations thereon. Here, we present ab initio molecular dynamics simulations of a hydrated dielectron with or without explicit Li+ or Cs+ counterions. While the overall solvation structure is preserved in all these systems, the presence of cations has a distinct effect of increasing the dielectron gyration radius by about 6% and forming cation-specific cation−dielectron arrangements. Moreover, analysis of water bond lengths reveals in all studied systems a substantial elongation of first-shell O−H bonds oriented toward the dielectron, providing a structural explanation for vibrational red shifts observed in resonance Raman measurements. Finally, at the 10 ps simulation time scale, rare reactive events were observed, albeit only for the system without metal cations, where hydride intermediates stable on picosecond time scales were identified. These observations also suggest that, on the investigated time scales, metal cations may suppress hydrated dielectron reactivity.