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Distinguishing mechanisms behind the droplet-size dependence of the Na+–He attachment rate

Ascertain the dominant mechanism, or quantify the relative contributions, responsible for the observed increase of the helium attachment rate r with helium nanodroplet size in the Poisson analysis of Na+He_n yields—specifically: (i) determine whether longer lift-off times t_lift in larger droplets allow additional binding and dissipation before ejection; (ii) determine whether larger droplets dissipate solvation energy faster due to their higher density of states; and (iii) determine whether softer Coulomb repulsion in larger droplets reduces vibrational excitation and thus post-ejection evaporation of Na+He_N complexes, leading to apparent larger detected n at earlier times.

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Background

The experiment measures femtosecond-resolved solvation of a Na+ ion in helium nanodroplets by monitoring time-dependent yields of Na+He_n complexes and fitting a Poisson process to extract a helium attachment rate r. Measurements across three droplet sizes (N_D = 3600, 5200, 9000) show that r increases with droplet size.

The authors propose three specific mechanisms that could explain the size dependence: (i) larger droplets lead to longer lift-off times t_lift, giving Na+He_N more time for additional He attachment and energy dissipation before ejection; (ii) larger droplets, having higher density of states, may dissipate the solvation energy more quickly; and (iii) the softer Coulomb explosion in larger droplets may impart less vibrational energy to the ejected complexes, reducing post-ejection evaporation and thereby biasing detection toward larger n at earlier times. They explicitly state that they cannot distinguish between these three mechanisms in the present work.

References

The fit also shows that the helium attachment rate increases when the droplet size increases. This could be because the increase of $t_\text{lift}$ with droplet size leaves \ce{Na+He_$N$} more time to pick up additional He atoms and to dissipate energy for larger complexes. Another explanation for this observation is that larger droplets may be able to dissipate the solvation energy faster since the density of states in the droplet increases with size. Thirdly, the softer Coulomb explosion for the larger droplets will add less vibrational energy to the ejected \ce{Na+He_{$N$} ions. As such, the ions will have a smaller probability for evaporating He atoms, which in turn leads to detection of larger \ce{Na+He_{$n$} complexes at earlier times. Currently, we are not able to distinguish between these three mechanisms.

Femtosecond-and-atom-resolved solvation dynamics of a Na$^+$ ion in a helium nanodroplet (2502.11783 - Albrechtsen et al., 17 Feb 2025) in Section 'Results and discussion' → Subsection 'Attachment rate of He atoms', paragraph discussing droplet-size effects; immediately after Table 'tab:poissonResults' (around Fig. nDist_comparison)