Time-resolved solvation of alkali ions in superfluid helium nanodroplets

Solvatation résolue en temps d'ions alcalins dans des nanogouttes d'hélium superfluides

Ernesto García-Alfonso (1, 2) , Manuel Barranco (3) , Nadine Halberstadt (1, 2) , Martí Pi (3)

1 LCAR - Laboratoire Collisions Agrégats Réactivité
2 THE-LCAR - Théorie (LCAR)
3 IN2UB - Institute of Nanoscience and Nanotechnology

The sinking of alkali cations in superfluid 4He nanodroplets is investigated theoretically using liquid 4He time-dependent density functional theory at zero temperature. The simulations illustrate the dynamics of the buildup of the first solvation shell around the ions. The number of helium atoms in this shell is found to linearly increase with time during the first stages of the dynamics. This points to a Poissonian capture process, as concluded in the work of Albrechtsen et al. on the primary steps of Na+ solvation in helium droplets [Albrechtsen et al., Nature 623, 319 (2023)]. The energy dissipation rate by helium atom ejection is found to be quite similar between all alkalis, the main difference being a larger energy dissipated per atom for the lighter alkalis at the beginning of the dynamics. In addition, the number of helium atoms in the first solvation shell is found to be lower at the end of the dynamics than at equilibrium for both Li+ and Na+, pointing to a kinetic rather than thermodynamical control of the snowball size for small and strongly attractive ions.

Mots clés: Superfluid helium nanodroplets; Ion solvation; Quantum time-dependent simulations; Poissonian mechanism; Kinetic control; helium snowball

Domaines: Chimie-Physique [physics.chem-ph]

Ernesto García-Alfonso, Manuel Barranco, Nadine Halberstadt, Martí Pi. Time-resolved solvation of alkali ions in superfluid helium nanodroplets. Journal of Chemical Physics, 2024, 160 (16), pp.164308. ⟨10.1063/5.0205951⟩. ⟨hal-04556577⟩