▪ Abstract Laser ablation of in situ metals has recently made it possible to immerse a large number of different metal atoms and ions and small clusters of metal atoms in liquid helium (He) and thus study their absorption and emission spectra in the visible region. Atoms and molecules are readily picked up by large ( ≥ 103 atoms) He droplets, and their spectra are sensitively detected through the use of either beam depletion following absorption or laser-induced fluorescence. Within the past three years, a wide variety of molecules, ranging from OCS to large organic molecules such as amino acids and a number of van der Waals complexes and even large metal clusters, have been embedded in He droplets and studied either in infrared or in the visible region. These results are discussed here in detail, and the evidence for the effect of superfluidity on the spectral features is reviewed.

Spectroscopy of atoms and molecules in liquid helium

Recent experiments on the electronic spectroscopy of atoms, clusters, and organic molecules embedded in helium nanodroplets are reviewed. Electronic transitions imply a larger degree of distortion of the helium environment as compared to vibrational and rotational excitations. Thus new phenomena arise such as the appearance of side bands in the spectra, which are due to the excitation of helium collective vibrations, large changes of the effective molecular rotational constants and even the expulsion of an atom (or molecule) from the cluster upon excitation. These features make it possible to probe the helium environment and its interactions with molecular chromophores on the atomic scale. Real-time studies of the manifestations of superfluidity and of chemical processes in the droplets via femtosecond excitation techniques, provide a new perspective to this field. The considerable amount of data available so far shows the large potential of helium droplets for isolation and spectroscopy of large molecule...

Electronic spectroscopy in He droplets

In this report I will review experimental studies of free helium droplets, with the exception of spectroscopic studies of helium droplets that contain impurities. This particular topic, as well as theoretical studies of helium droplets, will be reviewed separately elsewhere in this issue.

Experimental studies of helium droplets

Helium nanodroplets, commonly regarded as the ‘nearly ideal spectroscopic matrix’, are being actively studied for more than two decades now While they mostly serve as cold, weakly perturbing and transparent medium for high-resolution spectroscopy of embedded molecules, their intrinsic quantum properties such as microscopic superfluidity still are subject-matter of current research This article reviews recent work on pure and doped He nanodroplets using photoionisation (PI) spectroscopy, an approach which has greatly advanced in the past years While the notion of the ideal spectroscopic matrix mostly no longer holds in this context, PI techniques provide detailed insights into the photo-physical properties of pure and doped He nanodroplets and their relaxation dynamics following electronic excitation Exploiting nowadays available high laser fields, even highly ionised states of matter on the nanoscale can be formed Our particular focus lies on recent experimental progress including femtosecond time-re

Photoionisaton of pure and doped helium nanodroplets

Liquid helium droplets of initial mean cluster size, 〈N〉, ranging from 600 to 8000 atoms are doped with argon using the pick-up technique. The doped clusters are ionized by electron impact, and the resulting fragment ions are monitored as a function of argon pressure in the pick-up volume. Analysis of the pressure dependent ion signals is used to determine (1) the probability for charge transfer from He+ to the Ar atoms within the droplet, and (2) the probability for fragmentation of the Ark subclusters upon ionization. The measured charge transfer probability from He+ to Ar ranges from 0.05±0.02 for clusters of mean original size 〈N〉=8000 to 0.26±0.05 for 〈N〉=600. Charge transfer to the Ark constituent results in the following qualitative trends; a single Ar atom yields HenAr+ ions; Ar2 mainly yields Ar2+, and Ar3 mainly fragments to yield Ar2+. Simulations of the results are performed to extract information on how the charge transfer and fragmentation processes within the ionized droplet dependent on th...

Capture and ionization of argon within liquid helium droplets

The photoionization of neutral liquid helium droplets (mean particle number 〈N〉=102–107) was studied using synchrotron radiation at photon energies ranging from 15 to 30 eV. Mass spectra as well as total and mass selective ion yields were measured as a function of the photon energy for different droplet sizes. The experiments indicate that ionization occurs not only by a direct process at photon energies above the atomic ionization potential but also at energies below the threshold by an autoionization process. The latter ionization mechanism proceeds via the electronically excited states of the neutral droplet, which show a strong neutral droplet size dependence. For large neutral droplets HeN(〈N〉≳104) retarding field measurements established that a predominant part of the total ion yield results from larger cluster ions He+k(k≳103). These measurements also show that a decay by fluorescence emission is much more probable than one by ionization following the photoexcitation process. In droplets with embed...

M. Fieber‐Erdmann

Papers

The photoionization of large pure and doped helium droplets