Stefan E. Huber

Detection of Negative Charge Carriers in Superfluid Helium Droplets: The Metastable Anions He* − and He 2 * −

Helium droplets provide the possibility to study phenomena at the very low temperatures at which quantum mechanical effects are more pronounced and fewer quantum states have significant occupation probabilities. Understanding the migration of either positive or negative charges in liquid helium is essential to comprehend charge-induced processes in molecular systems embedded in helium droplets. Here, we report the resonant formation of excited metastable atomic and molecular helium anions in superfluid helium droplets upon electron impact. Although the molecular anion is heliophobic and migrates toward the surface of the helium droplet, the excited metastable atomic helium anion is bound within the helium droplet and exhibits high mobility. The atomic anion is shown to be responsible for the formation of molecular dopant anions upon charge transfer and thus, we clarify the nature of the previously unidentified fast exotic negative charge carrier found in bulk liquid helium.

On the properties of charged and neutral, atomic and molecular helium species in helium nanodroplets: interpreting recent experiments

Properties of ground state , , and excited (metastable) , , and are calculated using the coupled-cluster method and basis sets multiply augmented with diffuse functions. The aim of this work is to capture the essential physics needed to describe the qualitatively different behaviour of the above mentioned helium species dissolved in liquid helium. By studying their interaction with atomic ground state helium it is found that ground state He, He+, He2+ and excited (metastable) He*− are well bound within a helium droplet. In comparison excited (metastable) He*, He2* and He2*− are found to be squeezed out due to the high energetic cost associated with the large volume they require inside a helium droplet. In particular, the molecular species He2* and He2*− consist of a positive core in the form of a He2+ which is surrounded by a diffuse electronic cloud accounting for one or two electrons, respectively. The implications of these results for recent experimental studies on helium nanodroplets are discussed, particularly for the negatively charged species He*− and He2*−. We find that the latter species experience completely different dynamcis in a helium droplet although they are very similar in various other respects (e.g. diffuse electron clouds, size) in good agreement with experimental observations.

Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule

We calculate harmonic frequencies of the three most abundant carbonic acid conformers. For this, different model chemistries are investigated with respect to their benefits and shortcomings. Based on these results we use perturbation theory to calculate anharmonic corrections at the {\omega}B97XD/aug-cc-pVXZ, X=D,T,Q, level of theory and compare them with recent experimental data and theoretical predictions. A discrete variable representation method is used to predict the large anharmonic contributions to the frequencies of the stretching vibrations in the hydrogen bonds in the carbonic acid dimer. Moreover, we re-investigate the energetics of the formation of the carbonic acid dimer from its constituents water and carbon dioxide using a high-level extrapolation method. We find that the {\omega}B97XD functional performs well in estimating the fundamental frequencies of the carbonic acid conformers. Concerning the reaction energetics, the accuracy of {\omega}B97XD is even comparable to the high-level extrapolation method. We discuss possibilities to detect carbonic acid in various natural environments such as Earths and Martian atmospheres.

Formation of Dianions in Helium Nanodroplets

The formation of dianions in helium nanodroplets is reported for the first time. The fullerene cluster dianions (C60)n(2-) and (C70)n(2-) were observed by mass spectrometry for n≥5 when helium droplets containing the appropriate fullerene were subjected to electron impact at approximately 22 eV. A new mechanism for dianion formation is described, which involves a two-electron transfer from the metastable He(-) ion. As well as the prospect of studying other dianions at low temperature using helium nanodroplets, this work opens up the possibility of a wider investigation of the chemistry of He(-), a new electron-donating reagent.

On the formation of (anionic) excited helium dimers in helium droplets.

Metastable atomic and molecular helium anions exhibiting high-spin quartet configurations can be produced in helium droplets via electron impact. Their lifetimes allow detection in mass spectrometric experiments. Formation of atomic helium anions comprises collision-induced excitation of ground state helium and concomitant electron capture. Yet the formation of molecular helium anions in helium droplets has been an unresolved issue. In this work, we explore the interaction of excited helium atoms exhibiting high-spin triplet configurations with ground state helium using the equation-of-motion coupled-cluster method. Transition barriers in the energetically lowest He*–He and He*––He interaction potentials prevent molecule formation at the extremely low temperatures present in helium droplets. In contrast, some excited states allow a barrier-free formation of molecular helium (anions). Moreover, we show that the necessary excitation energies pinpoint (higher) resonances in recently recorded mass spectra and emend the assignment of those resonances that have previously been assigned to electron-impact ionization of ground state helium necessitating subsequent double-electron capture. Embedding molecules or molecular clusters in helium droplets is a predestined experimental technique for the study of phenomena at very low temperatures. Profound knowledge about active processes in the helium environment is required for a proper assessment of experimental data.

Permeation of low-Z atoms through carbon sheets: Density functional theory study on energy barriers and deformation effects

Energetic and geometric aspects of the permeation of the atoms hydrogen to neon neutral atoms through graphene sheets are investigated by investigating the associated energy barriers and sheet deformations. Density functional theory calculations on cluster models, where graphene is modeled by planar polycyclic aromatic hydrocarbons (PAHs), provide the energies and geometries. Particularities of our systems, such as convergence of both energy barriers and deformation curves with increasing size of the PAHs, are discussed. Three different interaction regimes, adiabatic, planar and vertical, are investigated by enforcing different geometrical constraints. The adiabatic energy barriers range from 5 eV for hydrogen to 20 eV for neon. We find that the permeation of oxygen and carbon into graphene is facilitated by temporary chemical bonding while for other, in principle reactive atoms, it is not. We discuss implications of our results for modeling chemical sputtering of graphite.

Dissociative Electron Attachment to β‐Alanine

A detailed study on dissociative electron attachment (DEA) to β-alanine (βA) in the gas phase is presented. Ion yields as a function of the incident electron energy from about 0 to 15 eV have been measured for most of the fragments. As for all α-amino acids, the main reaction corresponds to the loss of a hydrogen atom, although many other fragments have been observed that involved more complex bond cleavages. Threshold energies have been calculated by using the G4(MP2) method for various decomposition reactions. Fragmentation pathways were also investigated to measure metastable decays of the intermediate fragment anion (βA-H)(-) by using the mass-analyzed ion kinetic energy (MIKE) scan technique. Comparisons with α-alanine and other amino acids are made when relevant.

Upper Limits to the Reaction Rate Coefficients of Cn– and CnH– (n = 2, 4, 6) with Molecular Hydrogen

In the interstellar medium (ISM) ion–molecule reactions play a key role in forming complex molecules. Since 2006, after the radioastronomical discovery of the first of by now six interstellar anions, interest has grown in understanding the formation and destruction pathways of negative ions in the ISM. Experiments have focused on reactions and photodetachment of the identified negatively charged ions. Hints were found that the reactions of CnH(–) with H2 may proceed with a low (<10(–13) cm(3) s(–1)), but finite rate [Eichelberger, B.; et al. Astrophys. J. 2007, 667, 1283]. Because of the high abundance of molecular hydrogen in the ISM, a precise knowledge of the reaction rate is needed for a better understanding of the low-temperature chemistry in the ISM. A suitable tool to analyze rare reactions is the 22-pole radiofrequency ion trap. Here, we report on reaction rates for Cn(–) and CnH(–) (n = 2, 4, 6) with buffer gas temperatures of H2 at 12 and 300 K. Our experiments show the absence of these reactions with an upper limit to the rate coefficients between 4 × 10(–16) and 5 × 10(–15) cm(3) s(–1), except for the case of C2(–), which does react with a finite rate with H2 at low temperatures. For the cases of C2H(–) and C4H(–), the experimental results were confirmed with quantum chemical calculations. In addition, the possible influence of a residual reactivity on the abundance of C4H(–) and C6H(–) in the ISM were estimated on the basis of a gas-phase chemical model based on the KIDA database. We found that the simulated ion abundances are already unaffected if reaction rate coefficients with H2 were below 10(–14) cm(3) s(–1).

Low energy electron attachment to cyanamide (NH2CN)

Cyanamide (NH2CN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. In the present investigation, dissociative electron attachment to NH2CN has been studied in a crossed electron-molecular beams experiment in the electron energy range from about 0 eV to 14 eV. The following anionic species were detected: NHCN(-), NCN(-), CN(-), NH2(-), NH(-), and CH2(-). The anion formation proceeds within two broad electron energy regions, one between about 0.5 and 4.5 eV and a second between 4.5 and 12 eV. A discussion of possible reaction channels for all measured negative ions is provided. The experimental results are compared with calculations of the thermochemical thresholds of the anions observed. For the dehydrogenated parent anion, we explain the deviation between the experimental appearance energy of the anion with the calculated corresponding reaction threshold by electron attachment to the isomeric form of NH2CN--carbodiimide.

Electron-Induced Chemistry of Cobalt Tricarbonyl Nitrosyl (Co(CO)3NO) in Liquid Helium Nanodroplets.

Electron addition to cobalt tricarbonyl nitrosyl (Co(CO3NO) and its clusters has been explored in helium nanodroplets. Anions were formed by adding electrons with controlled energies, and reaction products were identified by mass spectrometry. Dissociative electron attachment (DEA) to the Co(CO)3NO monomer gave reaction products similar to those reported in earlier gas phase experiments. However, loss of NO was more prevalent than loss of CO, in marked contrast to the gas phase. Since the Co–N bond is significantly stronger than the Co–C bond, this preference for NO loss must be driven by selective reaction dynamics at low temperature. For [Co(CO)3NO]N clusters, the DEA chemistry is similar to that of the monomer, but the anion yields as a function of electron energy show large differences, with the relatively sharp resonances of the monomer being replaced by broad profiles peaking at much higher electron energies. A third experiment involved DEA of Co(CO)3NO on a C60 molecule in an attempt to simulate the effect of a surface. Once again, broad ion yield curves are seen, but CO loss now becomes the most probable reaction channel. The implication of these findings for understanding focused electron beam induced deposition of cobalt is described.