Fragmentation dynamics of Ar₄He₁₀₀₀ upon electron impact ionization: Competition between ion ejection and trapping

The fragmentation upon electron impact ionization of Ar₄He₁₀₀₀ is investigated by means of mixed quantum-classical dynamics simulations. The Ar₄ ⁺ dopant dynamics is described by a surface hopping method coupled with a diatomics-in-molecules model to properly take into account the multiple Ar₄ ⁺ electronic surfaces and possible transitions between them. Helium atoms are treated individually using zero-point averaged dynamics, a method based on the building of an effective He-He potential. Fast electronic relaxation is observed from less than 2 ps to ∼30 ps, depending on initial conditions. The main fragments observed are Ar₂ ⁺He_q and Ar₃ ⁺He_q (q ≤ 1000), with a strong contribution of the bare Ar₂ ⁺ ion, and neither Ar⁺ nor Ar⁺He_q fragments are found. The smaller fragments (q ≤ 50) are found to mostly come from ion ejection, whereas larger fragments (q > 500) originate from long-term ion trapping. Although the structure of the trapped Ar₂ ⁺ ions is the same as in the gas phase, trapped Ar₃ ⁺ and Ar₄ ⁺ are rather slightly bound Ar₂ ⁺⋯Ar and Ar₂ ⁺⋯Ar⋯Ar structures (i.e., an Ar₂ ⁺ core with one or two argon atoms roaming within the droplet). These loose structures can undergo geminate recombination and release Ar₃ ⁺He_q or Ar₄ ⁺He_q (q ≤ 50) in the gas phase and/or induce strong helium droplet evaporation. Finally, the translational energy of the fragment center of mass was found to be suitable to provide a clear signature of the broad variety of processes at play in our simulations.