Andrey F. Vilesov

Electronic spectroscopy in He droplets

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...

High-Resolution Molecular Spectroscopy of van der Waals Clusters in Liquid Helium Droplets

Small van der Waals clusters of sulfur hexafluoride (SF6) and mixed SF6-rare gas clusters were prepared inside large droplets of helium-4, with each droplet consisting of about 4000 helium atoms. A diode laser was used to measure the high-resolution infrared spectra of these clusters in the vicinity of the ν3 vibrational mode. In all cases rotational structure was observed, indicating that the embedded species rotate nearly freely, although they had been cooled to a temperature of 0.37 kelvin. The results indicate that helium droplets are probably superfluid and thereby provide a uniquely cold yet gentle matrix for high-resolution spectroscopy.

Shapes and vorticities of superfluid helium nanodroplets

X-raying superfluid helium droplets When physicists rotate the superfluid 4He, it develops a regular array of tiny whirlpools, called vortices. The same phenomenon should occur in helium droplets half a micrometer in size, but studying individual droplets is tricky. Gomez et al. used x-ray diffraction to deduce the shape of individual rotating droplets and image the resulting vortex patterns, which confirmed the superfluidity of the droplets. They found that superfluid droplets can host a surprising number of vortices and can rotate faster than normal droplets without disintegrating. Science, this issue p. 906 Vortex lattices inside individual helium droplets are imaged using x-ray diffraction. Helium nanodroplets are considered ideal model systems to explore quantum hydrodynamics in self-contained, isolated superfluids. However, exploring the dynamic properties of individual droplets is experimentally challenging. In this work, we used single-shot femtosecond x-ray coherent diffractive imaging to investigate the rotation of single, isolated superfluid helium-4 droplets containing ~108 to 1011 atoms. The formation of quantum vortex lattices inside the droplets is confirmed by observing characteristic Bragg patterns from xenon clusters trapped in the vortex cores. The vortex densities are up to five orders of magnitude larger than those observed in bulk liquid helium. The droplets exhibit large centrifugal deformations but retain axially symmetric shapes at angular velocities well beyond the stability range of viscous classical droplets.

Sizes of large He droplets

Helium droplets spanning a wide size range, N(He) = 10(3)-10(10), were formed in a continuous-nozzle beam expansion at different nozzle temperatures and a constant stagnation pressure of 20 bars. The average sizes of the droplets have been obtained by attenuation of the droplet beam through collisions with argon and helium gases at room temperature. The results obtained are in good agreement with previous measurements in the size range N(He) = 10(5)-10(7). Moreover, the measurements give the average sizes in the previously uncharacterized range of very large droplets of 10(7)-10(10) atoms. The droplet sizes and beam flux increase rapidly at nozzle temperatures below 6 K, which is ascribed to the formation of droplets within the nozzle interior. The mass spectra of the droplet beam upon electron impact ionization have also been obtained. The spectra show a large increase in the intensity of the He(4) (+) signal upon increase of the droplet size, an effect which can be used as a secondary size standard in the droplet size range N(He) = 10(4)-10(9) atoms.

Use of helium nanodroplets for assembly, transport, and surface deposition of large molecular and atomic clusters

The utility of continuous beam of helium droplets for assembly, transport, and surface deposition of metal and molecular clusters is studied. Clusters of propyne having from about 10 to 10(4) molecules were obtained via sequential pickup of molecules by He droplets with average sizes in the range of 10(4)-10(7) atoms. The maximum attainable flux of the propyne molecules carried by He droplets was found to be in the range of (5-15)x10(15) molecules sr(-1) s(-1), being larger in larger droplets. The size of the clusters and the flux of the transported species are ultimately limited by the evaporative extinction of the entire helium droplet upon capture of particles. It is shown that the attenuation of the He droplet beam in the process of the cluster growth can be used in order to obtain the average size and the binding energy of the clusters. Furthermore, we used He droplets for assembling and surface deposition of gold and silver clusters having about 500 atoms. Typical deposition rate of metal atoms of about 3 x 10(15) atoms sr(-1) s(-1) is comparable to or larger than obtained with other beam deposition techniques. We propose that doping of He droplets by Au and Ag atoms in two separate pickup chambers leads to formation of the bimetal clusters having core-shell structure.

Spectrum and infrared intensities of OH-stretching bands of water dimers

Water dimers have been assembled in He droplets and studied by infrared laser depletion spectroscopy. All four OH stretching bands of the dimer have been identified in the spectral range 3590-3800 cm(-1). Infrared intensities of the bands are also reported. The results are compared with previous measurements and theoretical calculations.

Infrared intensity in small ammonia and water clusters

Helium droplet technique has been used in order to measure the strength of the infrared absorption in small ammonia and water clusters as a function of size. Hydrogen bonding in ammonia and water dimers causes an enhancement of the intensity of the hydrogen stretching bands by a factor of four and three, respectively. Two types of the hydrogen bonded clusters show different size dependence of the infrared intensity per hydrogen bond. In ammonia (NH3)2 and (NH3)3 it is close to the crystal value. In water clusters, it increases monotonically with cluster size being in tetramers, a factor of two smaller than in the ice. The measured infrared intensity in water clusters is found to be a factor of two to three smaller as compared to the results of numerical calculations.

Manipulating and enhancing chemical reactions in helium droplets

The rate of the chemiluminescent Ba+N2O→BaO*+N2 reaction is greatly enhanced inside cold (0.38 K) helium droplets. If Xe atoms are added to the droplets, the “hot” surface channel is suppressed and all the emission is in a vibrational progression of sharp lines, indicating that the reaction occurs only inside the droplets.

Surface Deposition and Imaging of Large Ag Clusters Formed in He Droplets

The utility of a continuous beam of He droplets for the assembly and surface deposition of Ag(N) clusters, ~ 300-6000, is studied with transmission electron microscopy. Images of the clusters on amorphous carbon substrates obtained at short deposition times have provided for a measure of the size distribution of the metal clusters. The average sizes of the deposited clusters are in good agreement with an energy balance based estimate of Ag(N) cluster growth in He droplets. Measurements of the deposition rate indicate that upon impact with the surface the He-embedded cluster is attached with high probability. The stability of the deposited clusters on the substrate is discussed.

Intense pulsed helium droplet beams

Pulsed (30–100 μs) nozzle beams have been used to generate helium droplets (〈N〉=104–105). The dependence of the beam intensity and the mean droplet size on the source stagnation pressure and temperature are studied via mass spectroscopy and laser induced fluorescence of embedded phthalocyanine molecules. In comparison to a cw beam the pulsed source for the same pressure and temperature has a factor of 100 higher flux and the droplet sizes are 1 order of a magnitude larger.