Helium nanodroplets can serve as reaction containers for photoinduced time-resolved studies of cold, isolated molecular systems that are otherwise inaccessible. Recently, three different dynamical processes, triggered by photoexcitation of a single atom inside a droplet, were observed in their natural time scale: Expansion of the He solvation shell (He bubble) within 600 fs initiates a collective bubble oscillation with a ∼30 ps oscillation period, followed by dopant ejection after ∼60 ps. Here, we present a systematic investigation of these processes by combining time-resolved photoelectron and photoion spectroscopy with time-dependent He density functional theory simulations. By variation of the photoexcitation energy, we find that the full excess excitation energy, represented by the blue-shifted in-droplet excitation band, is completely transferred to the He environment during the bubble expansion. Surprisingly, we find that variation of the droplet size has only a minor influence on the ejection time, providing insight into the spatial distribution of the ground-state atoms before photoexcitation. Simulated particle trajectories after photoexcitation are in agreement with experimental observations and suggest that the majority of ground-state atoms are located at around 16 Å below the droplet surface. Bubble expansion and oscillation are purely local effects, depending only on the ultimate dopant environment. These solvation-induced dynamics will be superimposed on intramolecular dynamics of molecular systems, and a mechanistic description is fundamental for the interpretation of future experiments.
Ultrafast photoinduced dynamics of single atoms solvated inside helium nanodroplets
Note: This paper is part of the JCP Special Topic on Ultrafast Molecular Sciences by Femtosecond Photons and Electrons.
Bernhard Thaler, Pascal Heim, Leonhard Treiber, Markus Koch; Ultrafast photoinduced dynamics of single atoms solvated inside helium nanodroplets. J. Chem. Phys. 7 January 2020; 152 (1): 014307. https://doi.org/10.1063/1.5130145
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