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Helium nanodroplets are widely used as a cold, weakly interacting matrix forspectroscopy of embedded species. In this work we excite or ionize doped Hedroplets using synchrotron radiation and study the effect onto the dopant atomsdepending on their location inside the droplets (rare gases) or outside at thedroplet surface (alkali metals). Using photoelectron-photoion coincidenceimaging spectroscopy at variable photon energies (20-25 eV), we compare therates of charge-transfer to Penning ionization of the dopants in the two cases.The surprising finding is that alkali metals, in contrast to the rare gases,are efficiently Penning ionized upon excitation of the (n=2)-bands of the hostdroplets. This indicates rapid migration of the excitation to the dropletsurface, followed by relaxation, and eventually energy transfer to the alkalidopants.

Penning ionization of doped helium nanodroplets following EUV excitation