Time-resolved solvation of alkali ions in superfluid helium nanodroplets: Theoretical simulationof a pump–probe study

The solvation process of an alkali ion (Na+, K+, Rb+, and Cs+) inside a superfluid 4He2000 nanodroplet is investigated theoretically using liquid 4He time-dependent density functional theory at zero temperature. We simulate both steps of the pump–probe experiment conducted on Na+ [Albrechtsen <em>et al.</em>, Nature <strong>623</strong>, 319 (2023)], where the alkali atom residing at the droplet surface is ionized by the pump pulse and its solvation is probed by ionizing a central xenon atom and detecting the expulsed Na+He<em>n </em>ions. Our results confirm the Poissonian model for the binding of the first five He atoms for the lighter Na+ and K+ alkalis, with a rate in good agreement with the more recent experimental results on Na+ [Albrechtsen <em>et al.</em>, J. Chem. Phys. <strong>162</strong>, 174309 (2025)]. For the probe step, we show that the ion takes several picoseconds to get out of the droplet. During this rather long time, the solvation structure around it is very hot and far from equilibrium, and it can gain or lose more He atoms. Surprisingly, analyzing the Na+ solvation structure energy reveals that it is not stable by itself during the first few picoseconds of the solvation process. After that, energy relaxation follows a Newton behavior, as found experimentally, but with a longer time delay, 5.0 ≤ <em>t</em>0 ≤ 6.5 ps vs 0.23 ± 0.06 ps, and characteristic time, 7.3 ≤ τ ≤ 16.5 ps vs 2.6 ± 0.4 ps. We conclude that the first instants of the solvation process are highly turbulent and that the solvation structure is stabilized only by the surrounding helium “solvent.”