Helium Droplets Research Articles

Impact and lifecycle of superfluid helium drops on a solid surface

Superfluid helium droplets impacting on a solid surface behave much differently than any other fluid. After a short period of initial spreading that is similar to classical fluids, superfluid helium drops quickly shrink and disappear as the superfluid drains out through a thin adsorbed layer of helium on the surface. The lifetime and contact angle of these drops is strongly temperature-dependent, and colder drops (with high superfluid fractions) maintain a constant contact angle throughout the contraction. Above ${T}_{l\phantom{\rule{0}{0ex}}a\phantom{\rule{0}{0ex}}m\phantom{\rule{0}{0ex}}b\phantom{\rule{0}{0ex}}d\phantom{\rule{0}{0ex}}a}$, helium spreads slowly like other classical fluids.

Rotating mixed He3−He4 nanodroplets

Mixed $^3$He-$^4$He droplets created by hydrodynamic instability of a cryogenic fluid-jet may acquire angular momentum during their passage through the nozzle of the experimental apparatus. These free-standing droplets cool down to very low temperatures undergoing isotopic segregation, developing a nearly pure $^3$He crust surrounding a very $^4$He-rich superfluid core. Here, the stability and appearance of rotating mixed helium droplets are investigated using Density Functional Theory for an isotopic composition that highlights, with some marked exceptions related to the existence of the superfluid inner core, the analogies with viscous rotating droplets.

Autoionization dynamics of helium nanodroplets resonantly excited by intense XUV laser pulses

The ionization dynamics of helium droplets irradiated by intense, femtosecond extreme ultraviolet (XUV) pulses is investigated in detail by photoelectron spectroscopy. Helium droplets are resonantly excited to atomic-like 2p states with a photon energy of 21.5 eV and autoionize by interatomic Coulombic decay (ICD). A complex evolution of the electron spectra as a function of droplet size (250 to 106 He atoms per droplet) and XUV intensity (109–1012 W cm−2) is observed, ranging from narrow atomic-like peaks that are due to binary autoionization, to an unstructured feature characteristic of electron emission from a nanoplasma. The experimental results are analyzed and interpreted with the help of a numerical simulation based on rate equations taking into account all relevant processes—multi-step ionization, electronic relaxation, ICD, secondary inelastic collisions, desorption of electronically excited atoms, and collective autoionization (CAI).

Helium droplet assisted synthesis of plasmonic Ag@ZnO core@shell nanoparticles

Plasmonic Ag@ZnO core@shell nanoparticles are formed by synthesis inside helium droplets with subsequent deposition and controlled oxidation. The particle size and shape can be controlled from spherical sub-10 nm particles to larger elongated structures. An advantage of the method is the complete absence of solvents, precursors, and other chemical agents. The obtained particle morphology and elemental composition have been analyzed by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS). The results reveal that the produced particles form a closed and homogeneous ZnO layer around a 2–3 nm Ag core with a uniform thickness of (1.33 ± 0.15) nm and (1.63 ± 0.31) nm for spherical and wire-like particles, respectively. The results are supported by ultraviolet photoelectron spectroscopy (UPS), which indicates a fully oxidized shell layer for the particles studied by STEM. The plasmonic properties of the produced spherical Ag@ZnO core@shell particles are investigated by two-photon photoelectron (2PPE) spectroscopy. Upon excitation of the localized surface plasmon resonance in Ag at around 3 eV, plasmonic enhancement leads to the liberation of electrons with high kinetic energy. This is observed for both Ag and Ag@ZnO particles, showing that even if a Ag cluster is covered by the ZnO layer, a plasmonic enhancement can be observed by photoelectron spectroscopy.

Infrared Spectroscopy of Water and Zundel Cations in Helium Nanodroplets.

Here, we show that electron impact ionization of helium (He) droplets doped with water molecules and clusters yield water and Zundel cations embedded in the droplets consisting of a few thousand helium atoms. Infrared spectra in the OH-stretching range were obtained using the release of the cations from the droplets upon laser excitation. The spectra in He droplets appear to have about a factor of 10 narrower bands and similar matrix shifts as compared to those obtained via tagging with He and Ar atoms. The results confirm the calculated structure of the free Zundel ion, where the proton is equidistant from the two water units. The effect of the He environment on the spectra of ions is discussed. The signal shows nonlinear laser pulse energy dependence consistent with the evaporation of the entire droplet upon multiple absorptions of infrared photons. This conclusion is supported by the model calculations of the efficiency of the cations' release vs laser flux.

Rotational Coherence Spectroscopy of Molecules in Helium Nanodroplets: Reconciling the Time and the Frequency Domains.

Alignment of OCS, CS_{2}, and I_{2} molecules embedded in helium nanodroplets is measured as a function of time following rotational excitation by a nonresonant, comparatively weak ps laser pulse. The distinct peaks in the power spectra, obtained by Fourier analysis, are used to determine the rotational, B, and centrifugal distortion, D, constants. For OCS, B and D match the values known from IR spectroscopy. For CS_{2} and I_{2}, they are the first experimental results reported. The alignment dynamics calculated from the gas-phase rotational Schrödinger equation, using the experimental in-droplet B and D values, agree in detail with the measurement for all three molecules. The rotational spectroscopy technique for molecules in helium droplets introduced here should apply to a range of molecules and complexes.

Fragmentation dynamics of Ar4He1000 upon electron impact ionization: Competition between ion ejection and trapping.

The fragmentation upon electron impact ionization of Ar4He1000 is investigated by means of mixed quantum-classical dynamics simulations. The Ar4 + dopant dynamics is described by a surface hopping method coupled with a diatomics-in-molecules model to properly take into account the multiple Ar4 + electronic surfaces and possible transitions between them. Helium atoms are treated individually using zero-point averaged dynamics, a method based on the building of an effective He-He potential. Fast electronic relaxation is observed from less than 2 ps to ∼30 ps, depending on initial conditions. The main fragments observed are Ar2 +Heq and Ar3 +Heq (q ≤ 1000), with a strong contribution of the bare Ar2 + ion, and neither Ar+ nor Ar+Heq fragments are found. The smaller fragments (q ≤ 50) are found to mostly come from ion ejection, whereas larger fragments (q > 500) originate from long-term ion trapping. Although the structure of the trapped Ar2 + ions is the same as in the gas phase, trapped Ar3 + and Ar4 + are rather slightly bound Ar2 +⋯Ar and Ar2 +⋯Ar⋯Ar structures (i.e., an Ar2 + core with one or two argon atoms roaming within the droplet). These loose structures can undergo geminate recombination and release Ar3 +Heq or Ar4 +Heq (q ≤ 50) in the gas phase and/or induce strong helium droplet evaporation. Finally, the translational energy of the fragment center of mass was found to be suitable to provide a clear signature of the broad variety of processes at play in our simulations.

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.

Ultrashort XUV pulse absorption spectroscopy of partially oxidized cobalt nanoparticles

High-order harmonic generation (HHG) based transient extreme ultraviolet (XUV) absorption spectroscopy is an emerging technique to trace photoinduced charge carrier dynamics in condensed phase materials with femtosecond and even attosecond temporal resolution and elemental specificity. However, its application to nanoparticulate samples that are relevant, for example, for novel photocatalytic light harvesting concepts, has been limited. This is in part due to the challenge to produce residual-free samples on ultrathin, XUV-transparent substrates as well as a widespread understanding that sparsely distributed nanoparticles do not provide sufficient contrast for XUV absorption measurements. Here, we present static XUV absorption spectra of partially oxidized Co nanowire-structures with diameters of approximately 4.5 nm and lengths between 10 and 40 nm, recorded with an ultrashort pulse HHG light source. Nanoparticles are synthesized by the agglomeration of Co atoms inside superfluid helium droplets, followed by surface deposition and oxidation in ambient air. The method is uniquely suited for residual-free synthesis of transition metal nanowires and their deposition on ultrathin substrates. Analysis by high-resolution transmission electron microscopy reveals the formation of CoO nanowires with regions of unoxidized Co in their interior. The nanoparticle samples are investigated in an HHG-driven ultrafast XUV absorption setup. Despite the low surface coverage of only 23%, the recorded spectrum exhibits a distinct absorption feature at the Co M2,3(2p) edge near 60 eV with a peak height of about 40 mOD. The results support the feasibility of table-top ultrafast transient XUV absorption studies of photoinduced dynamics in transition metal oxide nanoparticles with sub-monolayer surface coverage.

Cluster ion polymerization of serine and tryptophan, the water loss channel

We present an experimental study on the stability of cluster cations formed by the assembly of tryptophan or serine moelcules inside charged helium droplets and subsequent droplet evaporation. The stability is probed via collision induced dissociation and mass spectrometry. We focus on the neutral loss of 18 Da that was previously proposed to result in the formation of an amide bond in amino acid clusters. We show that the cluster cations formed by the neutral loss of 18 Da from protonated parent cluster ion precursors are softly, presumably van der Waals, bound similar to the parent and protonated parent cluster cations. Cluster cations formed after neutral loss of 18 Da from the parent cluster cations are strongly bound, indicating the formation of new covalent bonds. Even though we observe a signal at m/z corresponding to dipeptide cations, their collision induced dissociation fragmentation does not allow unambiguous identification of their structure, particularly the amide bond. Our study at cryogenic conditions of He droplets demonstrates that peptide formation by the cluster ion polymerization is not a barrierless process and the formation of amide bonds may depend on activation methods and available catalysts.Graphical abstract

An intense source for cold cluster ions of a specific composition.

The demand for nanoscale materials of ultra-high purity and narrow size distribution is addressed. Clusters of Au, C60, H2O, and serine are produced inside helium nanodroplets using a combination of ionization, mass filtering, collisions with atomic or molecular vapor, and electrostatic extraction, in a specific and novel sequence. The helium droplets are produced in an expansion of cold helium gas through a nozzle into vacuum. The droplets are ionized by electron bombardment and subjected to a mass filter. The ionic and mass-selected helium droplets are then guided through a vacuum chamber filled with atomic or molecular vapor where they collide and "pick up" the vapor. The dopants then agglomerate inside the helium droplets around charge centers to singly charged clusters. Evaporation of the helium droplets is induced by collisions in a helium-filled radio frequency (RF)-hexapole, which liberates the cluster ions from the host droplets. The clusters are analyzed with a time-of-flight mass spectrometer. It is demonstrated that using this sequence, the size distribution of the dopant cluster ions is distinctly narrower compared to ionization after pickup. Likewise, the ion cluster beam is more intense. The mass spectra show, as well, that ion clusters of the dopants can be produced with only few helium atoms attached, which will be important for messenger spectroscopy. All these findings are important for the scientific research of clusters and nanoscale materials in general.

Electron attachment and electron ionization of helium droplets containing clusters of C60 and formic acid

High-resolution mass spectra of helium droplets doped with C60 and formic acid (FA) are ionized by electrons. Positive ion mass spectra reveal cluster ions [(C60)pFAn]+ together with their hydrogenated and dehydrogenated counterparts. Also observed are ions containing one or more water (W) molecules. The abundance distributions of these ions reveal several interesting features: i) [(C60)pFAn]+ ions are more abundant than hydrogenated [(C60)pFAnH]+ ions even though the opposite is true in the absence of C60 (i.e. if p = 0); ii) although [C60FA]+ is the most abundant ion containing a single C60, multiple C60 suppress the [(C60)pFA]+ signal; iii) an enhanced stability of [(C60)pW1FA5H]+ and [(C60)pW2FA6H]+ mirrors that of [W1FA5H]+ and [W2FA6H]+, respectively. On the other hand, the enhanced stability of [C60FA6H]+ finds no parallel in the stability pattern of [FAnH]+ or FAn+. Negative ion mass spectra indicate a propensity for non-dissociated [(C60)pFAn]- anions if p ≥ 1 which contrasts with the dominance of dehydrogenated [FAn-H]- anions.

Production of cold molecular ions in superfluid helium droplets

SynopsisThe capability of helium droplets to isolate cryogenic molecular ions at a temperature of 0.4 K is exploited to observe ultracold molecular processes in the RIKEN Cryogenic Electrostatic (RICE) storage ring. The development of a pulsed droplet beam consisting of extremely large helium droplets up to 1011 atoms is a promising step to apply this unique and robust cooling method to a wide variety of molecular ions. Production of ions by photoionization of neutral species inside helium droplets will provide internally cold ions below the ring temperature of 4 K.

Shifting formic acid dimers into perspective: vibrational scrutiny in helium nanodroplets.

A metastable dimer of formic acid has been prepared inside superfluid helium nanodroplets and examined using IR spectroscopy and quantum chemical calculations. This dimer has one strong O-HO[double bond, length as m-dash]C hydrogen bond and one weak C[double bond, length as m-dash]OH-C bond, which is the same bonding motif that exists between adjacent molecules in catemer chains found in the crystalline phase. The strongly bound OH stretching vibration of the metastable dimer shows clear evidence of significant coupling to other vibrational modes, but it is far less extensive than that seen for the doubly hydrogen bonded global energy minimum dimer structure, which dominates in the gas phase but is not observed in helium droplets. The width and shape of the resonance pattern can be qualitatively reproduced by B3LYP-D3(BJ)/aVTZ VPT2 calculations, if additional intensity scaling is applied. However, it is the MP2/aVTZ level of theory that consistently provides the closest agreement between calculated (VPT2) and experimental frequencies for the OH stretching vibration in the formic acid monomer and metastable dimer.

Electron transfer mediated decay of alkali dimers attached to He nanodroplets.

Alkali metal dimers attached to the surface of helium nanodroplets are found to be efficiently doubly ionized by electron transfer mediated decay (ETMD) when photoionizing the helium droplets. This process is evidenced by detecting in coincidence two energetic ions created by Coulomb explosion and one low-kinetic energy electron. The kinetic energy spectra of ions and electrons are reproduced by simple model calculations based on diatomic potential energy curves, and are in agreement with ab initio calculations for the He-Na2 and He-KRb systems. This work demonstrates that ETMD is an important decay channel in heterogeneous nanosystems exposed to ionizing radiation.

Ionization of large helium nanodroplets

SynopsisWe have produced and mass-selected large, highly charged helium droplets containing up to 1010 He atoms and several tens of charges. They are stable with both multiple positive and negative charge carriers and are stabilized by losing small fragments of excess charge instead of disintegrating (highly asymmetric fission).

Electron Diffraction of Pyrene Nanoclusters Embedded in Superfluid Helium Droplets.

We report electron diffraction of pyrene nanoclusters embedded in superfluid helium droplets. Using a least-squares fitting procedure, we have been able to separate the contribution of helium from those of the pyrene nanoclusters and determine the most likely structures for dimers and trimers. We confirm that pyrene dimers form a parallel double-layer structure with an interlayer distance of 3.5 Å and suggest that pyrene trimers form a sandwich structure but that the molecular planes are not completely parallel. The relative contributions of the dimers and trimers are ∼6:1. This work is an extension of our effort of solving structures of biological molecules using serial single-molecule electron diffraction imaging. The success of electron diffraction from an all-light-atom sample embedded in helium droplets offers reassuring evidence of the feasibility of this approach.

Heterogeneous Clusters of Phthalocyanine and Water Prepared and Probed in Superfluid Helium Nanodroplets.

Superfluid helium nanodroplets comprised of thousands to millions of helium atoms can serve as a reactor for the synthesis of heterogeneous molecular clusters at cryogenic conditions. The cluster synthesis occurs via consecutive pick-up of the cluster building blocks by the helium droplet and their subsequent coalescence within the droplet. The effective collision cross section of the building blocks is determined by the helium droplet size and thus exceeds by orders of magnitude that of a reactive collision in the gas phase. Moreover, the cryogenic helium environment (at 0.38 K) as a host promotes the formation of metastable cluster configurations. The question arises as to the extent of the actual involvement of the helium environment in the cluster formation. The present study deals with clusters of single phthalocyanine (Pc) molecules with single water molecules. A large fluorophore such as Pc offers several sites where the water molecule can attach. The resulting isomeric variants of the Pc-H2O complex can be selectively identified by electronic spectroscopy. We compare the experimental electronic spectra of the Pc-H2O complex generated in superfluid helium nanodroplets with the results of quantum-chemical calculations on the same cluster but under gas-phase conditions. The number of isomeric variants observed in the helium droplet experiment comes out the same as that obtained from our gas-phase calculations.

Atomic Gold Ions Clustered with Noble Gases: Helium, Neon, Argon, Krypton, and Xenon.

High-resolution mass spectra of helium droplets doped with gold and ionized by electrons reveal HenAu+ cluster ions. Additional doping with heavy noble gases results in NenAu+, ArnAu+, KrnAu+, and XenAu+ cluster ions. The high stability predicted for covalently bonded Ar2Au+, Kr2Au+, and Xe2Au+ is reflected in their relatively high abundance. Surprisingly, the abundance of Ne2Au+, which is predicted to have zero covalent bonding character and no enhanced stability, features a local maximum, too. The predicted size and structure of complete solvation shells surrounding ions with essentially nondirectional bonding depends primarily on the ratio σ* of the ion-ligand versus the ligand-ligand distance. For Au+ solvated in helium and neon, the ratio σ* is slightly below 1, favoring icosahedral packing in agreement with a maximum observed in the corresponding abundance distributions at n = 12. HenAu+ appears to adopt two additional solvation shells of Ih symmetry, containing 20 and 12 atoms, respectively. For ArnAu+, with σ* ≈ 0.67, one would expect a solvation shell of octahedral symmetry, in agreement with an enhanced ion abundance at n = 6. Another anomaly in the ion abundance at Ar9Au+ matches a local maximum in its computed dissociation energy.

Doping with multiple cations and failure of charge transfer in large ionized helium droplets.

We report experimental observations of aniline (A) cations and He2 + when aniline is doped into ionized helium droplets. Large droplets containing 108 atoms are bombarded by energetic electrons, resulting in more than one positive charge in one droplet. When aniline encounters the charged droplets, some are ionized via charge transfer, while others can remain neutral in the presence of He2 + when the mass-to-charge ratio (m/z) of the droplet is sufficiently large. Upon resonant excitation of the dopant An or An + (n ≥ 1), He2 + can be ejected. The excitation spectrum of He2 + becomes a juxtaposition of the spectra of An and An +. Moreover, an anticorrelation between the yields of He2 + and A+ is observed with increasing energies of the ionizing electrons. We attribute this result to the combined effect of reduction in m/z of the droplets and the different locations of He2 + and neutral An. Limited by the penetration depths of the ionizing electrons and further assisted by the Coulomb repulsion of coexisting cations, He2 + is located within 20 nm of the surface, while neutral An has an average position inside a large droplet. Upon resonant excitation of the interior An, He2 + is preferentially ejected. With increasing energies of the colliding electrons, the m/z of the droplets are reduced, leading to less effective charge shielding and more effective charge transfer, until ultimately, all He2 + can be neutralized to form A+.