Non-radiative decay and fragmentation in water molecules after 1 a 1-1 4 a 1 excitation and core ionization studied by electron-energy-resolved electron-ion coincidence spectroscopy

Abstract

<p>In this paper, we examine decay and fragmentation of core-excited and core-ionized water molecules combining quantum chemical calculations and electron-energy-resolved electron-ion coincidence spectroscopy. The experimental technique allows us to connect electronic decay from core-excited states, electronic transitions between ionic states, and dissociation of the molecular ion. To this end, we calculate the minimum energy dissociation path of the core-excited molecule and the potential energy surfaces of the molecular ion. Our measurements highlight the role of ultra-fast nuclear motion in the 1a1-14a1 core-excited molecule in the production of fragment ions. OH<sup>+</sup> fragments dominate for spectator Auger decay. Complete atomization after sequential fragmentation is also evident through detection of slow H<sup>+</sup> fragments. Additional measurements of the non-resonant Auger decay of the core-ionized molecule (1a1-1) to the lower-energy dication states show that the formation of the OH<sup>+</sup> + H<sup>+</sup> ion pair dominates, whereas sequential fragmentation OH<sup>+</sup> + H<sup>+</sup> → O + H<sup>+</sup> + H<sup>+</sup> is observed for transitions to higher dication states, supporting previous theoretical investigations.</p>