The relaxation dynamics of superexcited superfluid He nanodroplets is fully unravelled by means of extreme-ultraviolet (XUV) femtosecond electron and ion spectroscopy complemented by time-dependent density functional theory (TDDFT). Three main...

The autoionization dynamics of superexcited superfluid He nanodroplets doped with Na atoms is studied by extreme-ultraviolet (XUV) time-resolved electron spectroscopy. Following excitation into the higher-lying droplet absorption band, the droplet relaxes into the lowest metastable atomic 1s2s 1,3 S states from which interatomic Coulombic decay (ICD) takes place either between two excited He atoms or between an excited He atom and a Na atom attached to the droplet surface. Four main ICD channels are identified, and their decay times are determined by varying the delay between the XUV pulse and a UV pulse that ionizes the initial excited state and thereby quenches ICD. The decay times for the different channels all fall in the range of ∼1 ps, indicating that the ICD dynamics are mainly determined by the droplet environment. A periodic modulation of the transient ICD signals is tentatively attributed to the oscillation of the bubble forming around the localized He excitation.

Photoionization spectroscopy and mass spectrometry of doped helium (He) nanodroplets rely on the ability to efficiently detect ions and/or electrons. Using a commercial quadrupole mass spectrometer and a photoelectron–photoion coincidence spectrometer, we systematically measure yields of ions and electrons created in pure and doped He nanodroplets in a wide size range and in two ionization regimes—direct ionization and secondary ionization after resonant photoexcitation of the droplets. For two different types of dopants (oxygen molecules, O2, and lithium atoms, Li), we infer the optimal droplet size to maximize the yield of ejected ions. When dopants are ionized by charge-transfer to photoionized He nanodroplets, the highest yield of O2 and Li ions is detected for a mean size of ∼5×104 He atoms per nanodroplet. When dopants are Penning ionized via photoexcitation of the He droplets, the highest yield of O2 and Li ions is detected for ∼103 and ∼105 He atoms per droplet, respectively. At optimum droplet sizes, the detection efficiency of dopant ions in proportion to the number of primary photoabsorption events is up to 20% for charge-transfer ionization of O2 and 2% for Li, whereas for Penning ionization it is 1% for O2 and 4% for Li. Our results are instrumental in determining optimal conditions for mass spectrometric studies and photoionization spectroscopy of molecules and complexes isolated in He nanodroplets.

In this work, we present a new endstation for the AMOLine of the ASTRID2 synchrotron at Aarhus University, which combines a cluster and nanodroplet beam source with a velocity map imaging and time-of-flight spectrometer for coincidence imaging spectroscopy. Extreme-ultraviolet spectroscopy of free nanoparticles is a powerful tool for studying the photophysics and photochemistry of resonantly excited or ionized nanometer-sized condensed-phase systems. Here, we demonstrate this capability by performing photoelectron–photoion coincidence experiments with pure and doped superfluid helium nanodroplets. Different doping options and beam sources provide a versatile platform to generate various van der Waals clusters as well as He nanodroplets. We present a detailed characterization of the new setup and show examples of its use for measuring high-resolution yield spectra of charged particles, time-of-flight ion mass spectra, anion–cation coincidence spectra, multi-coincidence electron spectra, and angular distributions. A particular focus of the research with this new endstation is on intermolecular charge and energy-transfer processes in heterogeneous nanosystems induced by valence-shell excitation and ionization.

Superfluid helium nanodroplets are often considered as transparent and chemically inert nanometer-sized cryo-matrices for high-resolution or time-resolved spectroscopy of embedded molecules and clusters. However, resonant excitation with XUV radiation initiates...