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Sequential ionization of fullerene cluster ions (C$_{60}$)$_{n}^{+}$ within multiply-charged helium nanodroplets leads to the intriguing phenomenon of forming and stabilizing doubly- and triply-charged fullerene oligomers. Surprisingly, we have detected (C$_{60}$)$_{2}^{2+}$ and (C$_{60}$)$_{2}^{3+}$, indicating that dimers, rather than the previously established pentamers and dodecamers, are the smallest fullerene cluster sizes capable of stabilizing two and even three charges. This remarkable resilience against Coulomb explosion is achieved through efficient cooling within the superfluid environment of helium nanodroplets, and a sequential ionization scheme that populates covalently bound or physisorbed fullerene dimers. Calculations support the stability of four differently bonded (C$_{60}$)$_{2}^{2+}$ and (C$_{60}$)$_{2}^{3+}$ isomers and predict a low Coulomb barrier (<0.4 eV) preventing even dissociation of cold van der Waals complexes., Comment: 4 pages, 4 figures; supplemental material: 57 pages including calculated cartesian coordinates of optimized structures

High-resolution mass spectra of helium droplets doped with C$_{60}$ and formic acid (FA) are ionized by electrons. Positive ion mass spectra reveal cluster ions [(C$_{60}$)$_p$FA$_n$]$^+$ 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) [(C$_{60}$)$_p$FA$_n$]$^+$ ions are more abundant than hydrogenated [(C$_{60}$)$_p$FA$_n$H]$^+$ ions even though the opposite is true in the absence of C$_{60}$ (i.e. if $p$ = 0); ii) although [C$_{60}$FA]$^+$ is the most abundant ion containing a single C$_{60}$, multiple C$_{60}$ suppress the [(C$_{60}$)$_p$FA]$^+$ signal; iii) an enhanced stability of [(C$_{60}$)$_p$W$_1$FA$_5$H]$^+$ and [(C$_{60}$)$_p$W$_2$FA$_6$H]$^+$ mirrors that of [W$_1$FA$_5$H]$^+$ and [W$_2$FA$_6$H]$^+$, respectively. On the other hand, the enhanced stability of [C$_{60}$FA$_6$H]$^+$ finds no parallel in the stability pattern of [FA$_n$H]$^+$ or FA$_n$$^+$. Negative ion mass spectra indicate a propensity for non-dissociated [(C$_{60}$)$_p$FA$_n$]$^-$ anions if $p \geq 1$ which contrasts with the dominance of dehydrogenated [FA$_n$-H]$^-$ anions., Comment: 10 pages, 5 figures

Neon cluster ions Ne$_s^+$ grown in pre-ionized, mass-to-charge selected helium nanodroplets (HNDs) reveal a strong enrichment of the heavy isotope $^{22}$Ne that depends on cluster size s and the experimental conditions. For small sizes the enrichment is much larger than previously reported for bare neon clusters grown in nozzle expansions and subsequently ionized. The enrichment is traced to the massive evaporation of neon atoms in a collision cell that is used to strip helium from the HNDs. We derive a relation between the enrichment of $^{22}$Ne in the cluster ion and its corresponding depletion factor $F$ in the vapor phase. The value thus found for $F$ is in excellent agreement with a theoretical expression that relates isotopic fractionation in two-phase equilibria of atomic gases to the Debye temperature. Furthermore, the difference in zero-point energies between the two isotopes computed from F agrees reasonably well with theoretical studies of neon cluster ions that include nuclear quantum effects in the harmonic approximation. Another fitting parameter provides an estimate for the size s$_i$ of the precursor of the observed Ne$_s^+$. The value is in satisfactory agreement with the size estimated by modeling the growth of Ne$_s^+$, and with lower and upper limits deduced from other experimental data. On the other hand, neon clusters grown in neutral HNDs that are subsequently ionized by electron bombardment exhibit no statistically significant isotope enrichment at all. The finding suggests that the extent of ionization-induced dissociation of clusters embedded in HNDs is considerably smaller than for bare clusters., Comment: 14 pages, 5 figures, supplementary material

We use a novel technique to solvate silver cations in small clusters of noble gases. The technique involves formation of large, superfluid helium nanodroplets that are subsequently electron ionized, mass-selected by deflection in an electric field, and doped with silver atoms and noble gases (Ng) in pickup cells. Excess helium is then stripped from the doped nanodroplets by multiple collisions with helium gas at room temperature, producing cluster ions that contain no more than a few dozen noble gas atoms and just a few (or no) silver atoms. Under gentle stripping conditions helium atoms remain attached to the cluster ions, demonstrating their low vibrational temperature. Under harsher stripping conditions some of the heavier noble gas atoms will be evaporated as well, thus enriching stable clusters Ng$_n$Ag$_m^+$ at the expense of less stable ones. This results in local anomalies in the cluster ion abundance which is measured in a high-resolution time-of-flight mass spectrometer. Based on these data we identify specific "magic" sizes n of particularly stable ions. There is no evidence though for enhanced stability of Ng$_2$Ag$^+$, in contrast to the high stability of Ng$_2$Au$^+$ that derives from the covalent nature of the bond for heavy noble gases. "Magic" sizes are also identified for Ag$_2^+$ dimer ions complexed with He or Kr. Structural models will be tentatively proposed. A sequence of magic numbers $n$ = 12, 32, 44, indicative of three concentric solvation shells of icosahedral symmetry, is observed for He$_n$H$_2$O$^+$.

High-resolution mass spectra of helium droplets doped with gold and ionized by electrons reveal He$_n$Au$^+$ cluster ions. Additional doping with heavy noble gases results in NenAu+, Ar$_n$Au$^+$, Kr$_n$Au$^+$, and Xe$_n$Au$^+$ cluster ions. The high stability predicted for covalently bonded Ar$_2$Au$^+$, Kr$_2$Au$^+$, and Xe$_2$Au$^+$ is reflected in their relatively high abundance. Surprisingly, the abundance of Ne$_2$Au$^+$ 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 non-directional bonding depends primarily on the ratio $\sigma$* of the ion-ligand $versus$ the ligand-ligand distance. For Au$^+$ solvated in helium and neon the ratio $\sigma$* is slightly below 1, favoring icosahedral packing in agreement with a maximum observed in the corresponding abundance distributions at $n$ = 12. He$_n$Au$^+$ appears to adopt two additional solvation shells of $I_h$ symmetry, containing 20 and 12 atoms, respectively. For Ar$_n$Au$^+$, with $\sigma$* $\approx$ 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 Ar$_9$Au$^+$ matches a local maximum in its computed dissociation energy.

We demonstrate a novel method to ionize molecules or molecular clusters by proton transfer at temperatures below 1 K. The method yields nascent ions and largely eliminates secondary reactions, even for notoriously "delicate" molecules. Protonation is achieved inside liquid helium nanodroplets (HNDs) and begins with the formation of (H$_{2}$)$_{m}$H$^{+}$ ions as the proton donors. In a separate and subsequent step the HNDs are doped with a proton acceptor molecule, X. Proton transfer occurs between X and the cold proton donor ions inside a helium droplet, an approach that avoids the large excess energy that is released if HNDs are first doped and then ionized. Mass spectra, recorded after stripping excess helium and hydrogen in a collision cell, show that this method offers a new way to determine proton affinities of molecules and clusters by proton-transfer bracketing, to investigate astrochemically relevant ion-molecule reactions at sub-kelvin temperatures, and to prepare XH$^{+}$ ions that are suitable for messenger-tagging action spectroscopy., Comment: 9 pages, 4 figures, electronic supplementary information

Positively charged cluster ions of phosphorus were formed upon electron ionization of doped helium nanodroplets. The vapors of red phosphorus and a phosphate sample were picked up into neutral and charged helium nanodroplets. Independent on the conditions used, the cluster size distributions exhibit pronounced odd-even oscillations that are opposite to almost all experimental and theoretical patterns published in the literature. The low temperature environment of the superfluid He matrix quenches fragmentation and the charged phosphorus clusters resemble the structure of the neutral precursors., Comment: 12 pages, 6 figures

Helium tagging in action spectroscopy is an efficient method for measuring the absorption spectrum of complex molecular ions with minimal perturbations to the gas phase spectrum. We have used superfluid helium nanodroplets doped with corannulene to prepare cations of these molecules complexed with different numbers of He atoms. In total we identify 13 different absorption bands from corannulene cations between 5500 {\AA} and 6000 {\AA}. The He atoms cause a small, chemically induced redshift to the band positions of the corannulene ion. By studying this effect as a function of the number of solvating atoms we are able to identify the formation of solvation structures that are not visible in the mass spectrum. The solvation features detected with the action spectroscopy agree very well with the results of atomistic modeling based on path-integral molecular dynamics simulations. By additionally doping our He droplets with D$_2$, we produce protonated corannulene ions. The absorption spectrum of these ions differs significantly from the case of the radical cations as the numerous narrow bands are replaced by a broad absorption feature that spans nearly 2000 {\AA} in width., Comment: 10 pages, 7 figures, published in Faraday Discuissions

We have studied complexes of gold atoms and imidazole (C$_3$N$_2$H$_4$, abbreviated Im) produced in helium nanodroplets. Following the ionization of the doped droplets we detect a broad range of different Au$_m$Im$_n^+$ complexes, however we find that for specific values of $m$ certain $n$ are "magic" and thus particularly abundant. Our density functional theory calculations indicate that these abundant clusters sizes are partially the result of particularly stable complexes, e.g. AuIm$_2^+$, and partially due to a transition in fragmentation patterns from the loss of neutral imidazole molecules for large systems to the loss of neutral gold atoms for smaller systems., Comment: 7 pages, 9 figures, published in Physical Chemistry Chemical Physics

We report on the production and study of stable, highly charged droplets of superfluid helium. Using a novel experimental setup we produce neutral beams of liquid helium nanodroplets containing millions of atoms or more that can be ionized by electron impact, mass-per-charge selected, and ionized a second time before being analyzed. Droplets containing up to 55 net positive charges are identified and the appearance sizes of multiply charge droplets are determined as a function of charge state. We show that the droplets are stable on the millisecond time scale of the experiment and decay through the loss of small charged clusters, not through symmetric Coulomb explosions., Comment: 5 pages, 3 figures, published in Physical Review Letters

There has long been a discrepancy between the size distributions of Ar$_n^+$ clusters measured by different groups regarding whether or not magic numbers appear at sizes corresponding to the closure of icosahedral (sub-)shells. We show that the previously observed magic cluster size distributions are likely the result of an unresolved Ar$_n$H$^+$ component, that is, from protonated argon clusters. We find that the proton impurity gives cluster geometries that are much closer to those for neutral rare gas clusters, which are known to form icosahedral structures, than the pure cationic clusters, explaining why the mass spectra from protonated argon clusters better matches these structural models. Our results thus show that even small impurities, e.g.\ a single proton, can significantly influence the properties of clusters., Comment: 5 pages, 4 figures, published in Physical Review A

We report on a combined experimental and theoretical study of Li$^+$ ions solvated by up to 50 He atoms. The experiments show clear enhanced abundances associated with He$_n$Li$^+$ clusters where $n=2$, 6, 8, and 14. We find that classical methods, e.g.\ Basin-Hopping (BH), give results that qualitatively agree with quantum mechanical methods such as path integral Monte Carlo, diffusion Monte Carlo and quantum free energy, regarding both energies and the solvation structures that are formed. The theory identifies particularly stable structures for $n=4$, 6 and 8 which line up with some of the most abundant features in the experiments., Comment: 8 pages, 7 figures, published in Physical Chemistry Chemical Physics

We present a study of cationic and protonated clusters of neon and krypton. Recent studies using argon have shown that protonated rare gas clusters can have very different magic sizes than pure, cationic clusters. Here we find that neon behaves similarly to argon, but that the cationic krypton is more similar to its protonated counterparts than the lighter rare gases are, sharing many of the same magic numbers., Comment: 5 pages, 5 figures, accepted for publication in Journal of The American Society for Mass Spectrometry

Large ammonia clusters represent a model system of ices which are omnipresent throughout the space. The interaction of ammonia ices with other hydrogen-boding molecules such as methanol or water and their behavior upon an ionization are thus relevant in the astrochemical context. In this study, ammonia clusters (NH3)N with the mean size N ~230 were prepared in molecular beams and passed through a pickup cell in which methanol molecules were adsorbed. At the highest exploited pickup pressures, the average composition of (NH3)N(CH3OH)M clusters was estimated to be N:M ~210:10. On the other hand, the electron ionization of these clusters yielded about 75% of methanol-containing fragments (NH3)n(CH3OH)mH+ compared to 25% contribution of pure ammonia (NH3)nH+ ions. Based on this substantial disproportion, we propose the following ionization mechanism: The prevailing ammonia is ionized in most cases, resulting in NH+4 core solvated most likely with four ammonia molecules, yielding the well-known "magic number" structure (NH3)4NH+4 . The methanol molecules exhibit strong propensity for sticking to the fragment ion. We have also considered mechanisms of intracluster reactions. In most cases, proton transfer between ammonia units take place. The theoretical calculations suggested the proton transfer either from the methyl group or from the hydroxyl group of the ionized methanol molecule to ammonia to be the energetically open channels. However, the experiments with selectively deuterated methanols did not show any evidence for the D+ transfer from the CD3 group. The proton transfer from the hydroxyl group could not be excluded entirely nor confirmed unambiguously by the experiment., Comment: J Phys Chem

Interaction of NH$_3$$^{+}$ (ND$_3$$^{+}$) and NH$^{+}$ with a hydrocarbon-covered tungsten surface kept at room temperature and heated to 150{\deg}C and 300{\deg}C showed a series of reactions between the projectile ion and hydrocarbons adsorbed on the tungsten surface. Collisions with NH3+ and particularly with ND3+ showed formation of NH$_4$$^{+}$, HCNH$^{+}$, and CH$_2$NH$_2$$^{+}$ and ND$_3$H+, HCND$^{+}$, and CH$_2$ND$_2$$^{+}$, respectively, with NH$_4$$^{+}$ (ND$_3$H$^{+}$) strongly prevailing at low incident energies of the projectile ion. No formation of HCN$^{+}$ (DCN$^{+}$) could be positively identified. In reactions with NH$^{+}$ formation of HCN$^{+}$ was clearly observed; the dependence of the HCN$^{+}$ normalized ion yield on incident energy seems to indicate a threshold at about 40 eV which may be due to an activation energy or an endothermicity of the surface reaction of about 2.4-3.2 eV., Comment: 14 pages, 6 figures

Low energy electron attachment to mixed (H$_2$)$_x$/(O$_2$)$_y$ clusters and their deuterated analogues has been investigated for the first time. These experiments were carried out using liquid helium nanodroplets to form the clusters, and the effect of the added electron was then monitored via mass spectrometry. There are some important differences between electron attachment to the pure clusters and to the mixed clusters. A particularly notable feature is the formation of HO$_2$$^{-}$ and H$_2$O$^{-}$ ions from an electron-induced chemical reaction between the two dopants. The chemistry leading to these anions appears to be driven by electron resonances associated with H$_2$ rather than O$_2$. The electron resonances for H$_2$ can lead to dissociative electron attachment (DEA), just as for the free H$_2$ molecule. However, there is evidence that the resonance in H$_2$ can also lead to rapid electron transfer to O$_2$, which then induces DEA of the O$_2$. This kind of excitation transfer has not, as far as we are aware, been reported previously, Comment: 18 pages, 4 figures

Ion-molecule reactions between clusters of H$_2$/D$_2$ and O$_2$ in liquid helium nanodroplets were initiated by electron-induced ionization (at 70 eV). Reaction products were detected by mass spectrometry and can be explained by a primary reaction channel involving proton transfer from H$_3$$^{+}$ or H$_3$$^{+}$(H$_2$)$_n$ clusters and their deuterated equivalents. Very little HO$_2$$^{+}$ is seen from the reaction of H$_3$$^{+}$ with O$_2$, which is attributed to an efficient secondary reaction between HO$_2$$^{+}$ and H$_2$. On the other hand HO$_4$$^{+}$ is the most abundant product from the reaction of H$_3$$^{+}$ with oxygen dimer, (O$_2$)$_2$. The experimental data suggest that HO$_4$$^{+}$ is a particularly stable ion and this is consistent with recent theoretical studies of this ion., Comment: 16 pages, 3 figures

We report the first experimental study of the attachment of multiple foreign atoms to a cationic polycyclic aromatic hydrocarbon (PAH). The chosen PAH was coronene, C$_{24}$H$_{12}$, which was added to liquid helium nanodroplets and then subjected to electron bombardment. Using mass spectrometry, coronene cations decorated with helium atoms were clearly seen and the spectrum shows peaks with anomalously high intensities ("magic number" peaks), which represent ion-helium complexes with added stability. The data suggest formation of a rigid helium layer consisting of 38 helium atoms that completely covers both faces of the coronene ion. Additional magic numbers can be seen for the further addition of 3 and 6 helium atoms, which are thought to attach to the edge of the coronene. The observation of magic numbers for the addition of 38 and 44 helium atoms is in good agreement with a recent path integral Monte Carlo prediction for helium atoms on neutral coronene. An understanding of how atoms and molecules attach to PAH ions is important for a number of reasons including the potential role such complexes might play in the chemistry of the interstellar medium., Comment: 14 pages. 2 figures

Anions are formed by electron attachment to helium nanodroplets doped with N$_2$. The most prominent ion series is due to odd-numbered N$_m$$^{-}$ with 3 $\le$ m < 140. Neither N$^{-}$ nor N$_2$$^{-}$ are observed. An appearance energy of 11.5 $\pm$ 0.5 eV is measured for N$_3$$^{-}$. The yield of N$_m$$^{-}$ averaged over 5 $\le$ m $\le$ 21 shows an appearance energy of 9 eV, just above the estimated thermodynamic threshold for formation of N$_3$$^{-}$ from electron attachment to small N$_2$ clusters embedded in helium droplets. These findings support the notion that odd-numbered N$_m$$^{-}$ cluster ions are best characterized as N$_2$ van der Waals clusters with an azide anion chromophore but they are at odds with some theoretical reports. N$_3$$^{-}$(N$_2$)$_4$ and N$_3$$^{-}$(N$_2$)$_{11}$ form local maxima in the abundance distribution, suggesting that these ions are particularly stable. The yield of even-numbered N$_m$$^{-}$ ions (m $\ge$ 4) is two orders of magnitude lower, barely exceeding the background level. Several other cluster anion series are observed that involve impurities., Comment: 14 pages, 4 figures

Helium nanodroplets are doped with cesium and molecular hydrogen and subsequently ionized by electrons. Mass spectra reveal H$_x$Cs$^{+}$ ions that contain as many as 130 hydrogen atoms. Two features in the spectra are striking: First, the abundance of ions with an odd number of hydrogen atoms is very low; the abundance of HCs$^+$ is only 1 % that of H$_2$Cs$^+$. The dominance of even-numbered species is in stark contrast to previous studies of pure or doped hydrogen cluster ions. Second, the abundance of (H$_2$)$_n$Cs$^+$ features anomalies at n = 8, 12, 32, 44, and 52. Guided by previous work on ions solvated in hydrogen and helium we assign the anomalies at n = 12, 32, 44 to the formation of three concentric, solid-like solvation shells of icosahedral symmetry around Cs$^+$. Preliminary density functional theory calculations for n $\le$ 14 are reported as well., Comment: 14 pages, 5 figures

In 2015, Campbell et al. (Nature 523, 322) presented spectroscopic laboratory gas phase data for the fullerene cation, C$_{60}^+$, that coincide with reported astronomical spectra of two diffuse interstellar band (DIB) features at 9633 and 9578 \AA. In the following year additional laboratory spectra were linked to three other and weaker DIBs at 9428, 9366, and 9349 \AA. The laboratory data were obtained using wavelength-dependent photodissociation spectroscopy of small (up to three) He-tagged C$_{60}^+-$He$_n$ ion complexes, yielding rest wavelengths for the bare C$_{60}^+$ cation by correcting for the He-induced wavelength shifts. Here we present an alternative approach to derive the rest wavelengths of the four most prominent C$_{60}^+$ absorption features, using high resolution laser dissociation spectroscopy of C$_{60}^+$ embedded in ultracold He droplets. Accurate wavelengths of the bare fullerene cation are derived based on linear wavelength shifts recorded for He$_n$C$_{60}^+$ species with $n$ up to 32. A careful analysis of all available data results in precise rest wavelengths (in air) for the four most prominent C$_{60}^+$ bands: 9631.9(1) \AA, 9576.7(1) \AA, 9427.5(1) \AA, and 9364.9(1) \AA. The corresponding band widths have been derived and the relative band intensity ratios are discussed.

Hydrogen storage by physisorption in carbon based materials is hindered by low adsorption energies. In the last decade doping of carbon materials with alkali, earth alkali or other metal atoms was proposed as a means to enhance adsorption energies, and some experiments have shown promising results. We investigate the upper bounds of hydrogen storage capacities of $C_{60}Cs$ clusters grown in ultracold helium nanodroplets by analyzing anomalies in the ion abundance that indicate shell closure of hydrogen adsorption shells. On bare $C_{60}^{+}$, a commensurate phase with 32 $H_2$ molecules was identified in previous experiments. Doping $C_{60}$ with a single cesium atom leads to an increase in relative ion abundance for the first 10 $H_2$ molecules, and the closure of the commensurate phase is shifted from 32 to 42 $H_2$ molecules. Density functional theory calculations indicate that thirteen energetically enhanced adsorption sites exist, where six of them fill the groove between Cs and $C_{60}$ and 7 are located at the cesium atom. We emphasize the large effect of the quantum nature of the hydrogen molecule on the adsorption energies, i.e. the adsorption energies are decreased by around 50% for $(H_2)C_{60}Cs$ and up to 80% for $(H_2)C_{60}$ by harmonic zero-point corrections, which represent an upper bound to corrections for dissociation energies ($D_e$ to $D_0$) by the vibrational ground states. Five normal modes of libration and vibration of $H_2$ physisorbed on the substrate contribute primarily to this large decrease in adsorption energies. A similar effect can be found for H2 physisorbed on benzene and is expected to be found for any other weakly $H_2$-binding substrate.

The mechanism of ionization of helium droplets has been investigated in numerous reports but one observation has not found a satisfactory explanation: How are $He^+$ ions formed and ejected from undoped droplets at electron energies below the ionization threshold of the free atom? Does this path exist at all? A measurement of the ion yields of $He^+$ and $He_2^+$ as a function of electron energy, electron emission current, and droplet size reveals that metastable $He^{*-}$ anions play a crucial role in the formation of free $He^+$ at subthreshold energies. The proposed model is testable.

Electron ionization of helium droplets doped with cesium or potassium results in doubly and, for cesium, triply charged cluster ions. The smallest observable doubly charged clusters are $Cs_{9}^{2+}$ and $K_{11}^{2+}$; they are a factor two smaller than reported previously. The size of potassium dications approaches the Rayleigh limit nRay for which the fission barrier is calculated to vanish, i.e. their fissilities are close to 1. Cesium dications are even smaller than nRay, implying that their fissilities have been significantly overestimated. Triply charged cesium clusters as small as $Cs_{19}^{3+}$ are observed; they are a factor 2.6 smaller than previously reported. Mechanisms that may be responsible for enhanced formation of clusters with high fissilities are discussed.

We show, with both experiment and theory, that adsorption of $CO_2$ is sensitive to charge on a capturing model carbonaceous surface. In the experiment we dope superfluid helium droplets with $C_{60}$ and $CO_2$ and expose them to ionising free electrons. Both positively and negatively charged $C_{60}(CO_2)_n^{+/-}$ cluster ion distributions are observed with a high-resolution mass spectrometer and these show remarkable and reproducible anomalies in intensities that are strongly dependent on the charge. The highest adsorption capacity is seen with $C_{60}^+$. Complementary density functional theory calculations and molecular dynamics simulations provided insight into the nature of the interaction of charged $C_{60}$ with $CO_2$ as well as trends in the packing of $C_{60}^+$ and $C_{60}^-$. The quadrupole moment of $CO_2$ itself was seen to be decisive in determining the charge dependence of the observed adsorption features. Our findings are expected to apply to adsorption of $CO_2$ by charged surfaces in general.