Electron diffraction of 1,4-dichlorobenzene embedded in superfluid helium droplets.

We perform electron diffraction of 1,4-dichlorobenzene (C6H4Cl2, referred to as 2ClB) embedded in superfluid helium droplets to investigate the structure evolution of cluster growth. Multivariable linear regression fittings are used to determine the concentration and the best model structures of the clusters. At a droplet source temperature of 22 K with droplets containing on average 5000 He atoms, the fitting results agree with the doping statistics modeled using the Poisson distribution: the largest molecular clusters are tetramers, while the abundances of monomers and dimers are the highest and are similar. Molecular dimers of 2ClB are determined to have a parallel structure with a 60° rotation for the Cl-Cl molecular axes. However, a better agreement between experiment and fitting is obtained by reducing the interlayer distance that had been calculated using the density functional theory for dimers. Further calculations using the highest level quantum mechanical calculations prove that the reduction in interlayer distance does not significantly increase the energy of the dimer. Cluster trimers adopt a dimer structure with the additional monomer slanted against the dimer, and tetramers take on a stacked structure. The structure evolution with cluster size is extraordinary, because from trimer to tetramer, one monomer needs to be rearranged, and neither the trimer nor the tetramer adopts the corresponding global minimum structure obtained using high level coupled-cluster theory calculations. This phenomenon may be related to the fast cooling process in superfluid helium droplets during cluster formation.

Resolving the interlayer distance of cationic pyrene clusters embedded in superfluid helium droplets using electron diffraction.

We report the electron diffraction of cationic pyrene (C16H10) clusters embedded in superfluid helium droplets. The diffraction profile contains a significant contribution from helium, but interferences of atomic pairs of pyrene are still recognizable. From least-squares fittings, we determine an interlayer distance of 3.0 Å for the cationic cluster, shortened from 3.5 Å in neutral clusters. The relative contributions of dimers and trimers are about 2:1, in qualitative agreement with the doping statistics. Limited by the detection range of the experimental data, we cannot distinguish further structure details. The predominant contribution of helium also prevents observations of the solvation shell of the ionic cluster. Nevertheless, the success of this experiment demonstrates the feasibility of electron diffraction from an ionic all-light-atom system, dispelling the concern over limited particle concentration of ionic species in the diffraction region, and the need of heavy atoms for diffraction intensity.

Electron Diffraction of Ionic Argon Nanoclusters Embedded in Superfluid Helium Droplets.

We report electron diffraction of cationic argon nanoclusters embedded in superfluid helium droplets. Superfluid helium droplets are first doped with neutral argon atoms to form nanoclusters, and then the doped droplets are ionized by electrons. The much lower ionization energy of argon ensures that the positive charge resides on the Ar nanocluster. Using different stagnation temperatures and therefore droplets with different sizes, we have been able to preferentially form a small ionic cluster containing 2-4 Ar atoms and a larger cluster containing 7-11 atoms. The fitting results of the diffraction profiles agree with structures reported from theoretical calculations, containing a cationic trimer core with the remaining atoms largely neutral. This work testifies to the feasibility of performing electron diffraction from ionic species embedded in superfluid helium droplets, dispelling the concern over the particle density in the diffraction region. However, the large number of neutral helium atoms surrounding the cationic nanoclusters poses a challenge for the detection of the helium solvation layer, and the detection of which awaits further technological improvements.

Electron diffraction of CS2 nanoclusters embedded in superfluid helium droplets.

We report experimental results from electron diffraction of CS2 nanoclusters embedded in superfluid helium droplets. From detailed measurements of the sizes of doped droplets, we can model the doping statistics under different experimental conditions, thereby obtaining the range of cluster sizes of CS2. Using a least squares fitting procedure, we can then determine the structures and contributions of dimers, trimers, and tetramers embedded in small droplets. While dimers prefer a stable gas phase structure, trimers and tetramers seem to forgo the highly symmetric gas phase structures and prefer compact cuts from the crystalline structure of CS2. In larger droplets containing more than 12 CS2 monomers, the diffraction profile is consistent with a three-dimensional nanostructure of bulk CS2. This work demonstrates the feasibility of electron diffraction for in situ monitoring of nanocluster formation in superfluid helium droplets.

Suppression of Multiphoton Ionization of Aniline in Large Superfluid Helium Droplets.

We report suppression of multiphoton ionization (MPI) of aniline doped large superfluid helium droplets containing over 5 × 106 atoms. In contrast, surface-bound sodium atoms and dimers are readily desorbed and ionized. Adequacy of the experimental conditions is also confirmed from ejection of embedded aniline cations from smaller droplets containing multiple cations, and MPI of gaseous aniline. The photoelectrons have a mean-free-path of less than 1 nm and a thermalization distance of 10 nm. In a droplet with a diameter of over 70 nm, effective charge recombination within the droplet is expected.