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For sensitive studies of molecular ions in electrostatic storage rings, the exact knowledge of the isobaric composition of stored beams from a variety of ion sources is essential. Conventional mass-filtering techniques are often inefficient to resolve the beam components. Here, we report the first isochronous mass spectrometry in an electrostatic storage ring, which offers a high mass resolution of Δ m/ m < 1 × 10−5 even for heavy molecular species with m > 100 u and uncooled ion beams. Mass contaminations can be resolved and identified at relative fractions down to 0.02%.

Observations of CH$^+$ are used to trace the physical properties of diffuse clouds, but this requires an accurate understanding of the underlying CH$^+$ chemistry. Until this work, the most uncertain reaction in that chemistry was dissociative recombination (DR) of CH$^+$. Using an electron-ion merged-beams experiment at the Cryogenic Storage Ring, we have determined the DR rate coefficient of the CH$^+$ electronic, vibrational, and rotational ground state applicable for different diffuse cloud conditions. Our results reduce the previously unrecognized order-of-magnitude uncertainty in the CH$^+$ DR rate coefficient to $\sim \pm 20\%$ and are applicable at all temperatures relevant to diffuse clouds, ranging from quiescent gas to gas locally heated by processes such as shocks and turbulence. Based on a simple chemical network, we find that DR can be an important destruction mechanism at temperatures relevant to quiescent gas. As the temperature increases locally, DR can continue to be important up to temperatures of $ \sim 600\,\mathrm{K} $ if there is also a corresponding increase in the electron fraction of the gas. Our new CH$^+$ DR rate coefficient data will increase the reliability of future studies of diffuse cloud physical properties via CH$^+$ abundance observations., Comment: Main paper: PDFLaTeX with 7 pages, 3 figures. Appendix starting on page 7: PDFLaTeX with 11 pages, 2 figures, 4 tables. This article has been accepted by The Astrophysical Journal

Enhanced abundance of primordial HeH + Though only recently detected in space, the helium hydride ion (HeH + ) is thought to be the first molecule ever to have formed in the early Universe. Novotný et al. report state-specific rate coefficients for the dissociative reaction of HeH + with electrons, obtained using a cryogenic ion storage ring combined with a merged electron beam (see the Perspective by Bovino and Galli). They detect substantial rotational dependence and a decrease of the rates for the lowest states of HeH + , far below the values listed in astrochemistry databases and those previously applied in early-Universe models. These results suggest high abundance of this important primordial molecule at redshifts of first star and galaxy formation. Science , this issue p. 676 ; see also p. 639

The H 3 + ion is the simplest polyatomic molecule. Apart from its fundamental role as a benchmark system for theoretical calculations, it has attracted a lot of attention as one of the main drivers of an active interstellar ion-neutral chemistry network. H 3 + spectroscopy has contributed greatly to astrochemistry, and experiment and theory have both developed tremendously throughout the years, following the ground-breaking work by Oka. To date, the highest-lying identified H 3 + transitions were obtained using an action spectroscopy technique, employing stored H 3 + ions in a cryogenic ion trap. This approach was pioneered by Schlemmer and Gerlich for N 2 + , and is widely used today – in one form or another – for spectroscopic studies of interstellar ions. In this work, we explore the possibility to extend the range for H 3 + action spectroscopy even further, into the regime above 20 000 cm−1, in order to bridge the gap to the rich pre-dissociation spectrum of states near the dissociation limit that was obtained by Carrington et al. and remains unassigned after more than 30 years.

Photodetachment thermometry on a beam of OH$^-$ in a cryogenic storage ring cooled to below 10 K is carried out using two-dimensional, frequency and time dependent photodetachment spectroscopy over 20 minutes of ion storage. In equilibrium with the low-level blackbody field, we find an effective radiative temperature near 15 K with about 90% of all ions in the rotational ground state. We measure the J = 1 natural lifetime (about 193 s) and determine the OH$^-$ rotational transition dipole moment with 1.5% uncertainty. We also measure rotationally dependent relative near-threshold photodetachment cross sections for photodetachment thermometry., Manuscript LaTeX with 5 pages, 3 figures, and 1 table plus LaTeX supplement with 12 pages, 3 figures and 3 tables. This article has been accepted by Physical Review Letters

We have studied the photodissociation of CH^{+} in the Cryogenic Storage Ring at ambient temperatures below 10 K. Owing to the extremely high vacuum of the cryogenic environment, we were able to store CH^{+} beams with a kinetic energy of ∼60 keV for several minutes. Using a pulsed laser, we observed Feshbach-type near-threshold photodissociation resonances for the rotational levels J=0-2 of CH^{+}, exclusively. In comparison to updated, state-of-the-art calculations, we find excellent agreement in the relative intensities of the resonances for a given J, and we can extract time-dependent level populations. Thus, we can monitor the spontaneous relaxation of CH^{+} to its lowest rotational states and demonstrate the preparation of an internally cold beam of molecular ions.

We demonstrate the use of high power diode laser stacks to photodetach fast hydrogen and carbon anions and produce ground term neutral atomic beams. We achieve photodetachment efficiencies of $\sim$7.4\% for H$^-$ at a beam energy of 10\,keV and $\sim$3.7\% for C$^-$ at 28\,keV. The diode laser systems used here operate at 975\,nm and 808\,nm, respectively, and provide high continuous power levels of up to 2\,kW, without the need of additional enhancements like optical cavities. The alignment of the beams is straightforward and operation at constant power levels is very stable, while maintenance is minimal. We present a dedicated photodetachment setup that is suitable to efficiently neutralize the majority of stable negative ions in the periodic table.

The visible spectrum of H3+ is studied using high-sensitivity action spectroscopy in a cryogenic radiofrequency multipole trap. Advances are made to measure the weak ro-vibrational transitions from the lowest rotational states of H3+ up to high excitation energies providing visible line intensities and, after normalisation to an infrared calibration line, the corresponding Einstein $B$ coefficients. {\it Ab initio} predictions for the Einstein $B$ coefficients are obtained from a highly precise dipole moment surface of H3+ and found to be in excellent agreement, even in the region where states have been classified as chaotic.

We have investigated electron capture by NH+ resulting in dissociative recombination (DR). The impact energies studied of ~4–12 eV extend over the range below the two lowest predicted NH+ dissociative states in the Franck–Condon (FC) region of the ion. Our focus has been on the final state populations of the resulting N and H atoms. The neutral DR fragments are detected downstream of a merged electron and ion beam interaction zone in the TSR storage ring, which is located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. Transverse fragment distances were measured on a recently developed high count-rate imaging detector. The distance distributions enabled a detailed tracking of the final state populations as a function of the electron collision energy. These can be correlated with doubly excited neutral states in the FC region of the ion. At low electron energy of ~5 eV, the atomic product final levels are nitrogen Rydberg states together with ground-state hydrogen. In a small electron energy interval near 7 eV, a significant part of the final state population forms hydrogen Rydberg atoms with nitrogen atoms in the first excited (2D) term, showing the effect of Rydberg doubly excited states below the predicted 2 2Π ionic potential. The distance distributions above ~10 eV are compatible with nitrogen Rydberg states correlating to the doubly excited Rydberg state manifold below the ionic 2 4 Σ − level.

We have investigated dissociative recombination (DR) of NH$^+$ with electrons using a merged beams configuration at the TSR heavy-ion storage ring located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. We present our measured absolute merged beams recombination rate coefficient for collision energies from 0 to 12 eV. From these data we have extracted a cross section which we have transformed to a plasma rate coefficient for the collisional plasma temperature range from $T_{\rm pl} = 10$ to $18000$ K. We show that the NH$^+$ DR rate coefficient data in current astrochemical models are underestimated by up to a factor of $\sim 9$. Our new data will result in predicted NH$^+$ abundances lower than calculated by present models. This is in agreement with the sensitivity limits of all observations attempting to detect NH$^+$ in interstellar clouds., Comment: July 1st 2014: Accepted for publication in ApJ

Recent observations of H2 and H3+ in diffuse interstellar sightlines revealed a difference in the nuclear spin excitation temperatures of the two species. This discrepancy comes as a surprise, as H3+ and H2 should undergo frequent thermalizing collisions in molecular clouds. Non-thermal behavior of the fundamental H3+ / H2 collision system at low temperatures was considered as a possible cause for the observed irregular populations. Here, we present measurements of the steady-state ortho/para ratio of H3+ in collisions with H2 molecules in a temperature-variable radiofrequency ion trap between 45-100 K. The experimental results are close to the expected thermal outcome and they agree very well with a previous micro-canonical model. We briefly discuss the implications of the experimental results for the chemistry of the diffuse interstellar medium., Comment: 8 pages, 3 figures, 1 table, ApJ accepted

The cryogenic storage ring (CSR) for positive and negative atomic, molecular and cluster ions is starting operation at the Max Planck Institute for Nuclear Physics in Heidelberg.

We have experimentally investigated dissociative recombination of NH+ with electrons using a merged ion and electron beam configuration in a storage ring. A fast counting and position sensitive imaging detector enabled us to perform fragment imaging measurements over relative electron-ion collision energies from 0 to 12 eV. The results show unprecedented details on product excitation and on the reaction dynamics.

Storage ring studies of low energy electron collisions with molecular ions have been carried out for dissociative recombination (DR) of fluorine-bearing molecules. Here we report on work aiming to improve the understanding of astrochemistry involving HF, a possible spectroscopic tracer of interstellar H2. For CF+ the rate coefficient was obtained for temperatures down to 10 K. For D2F+ the DR fragmentation branching ratios were determined to be 66(3)%, 24(2)%, and 10(2)% for the F+D+D, DF+D, and D2+F channels, respectively. The molecular DR products of this reaction, DF and D2, display an unusually high level of internal excitation, close to their dissociation limit.

Combined experimental-theoretical study suggests facile formation of water in diffuse interstellar media., The gas-phase formation of water molecules in the diffuse interstellar medium (ISM) proceeds mainly via a series of reactions involving the molecular ions OH+, H2O+, and H3O+ and molecular hydrogen. These reactions form the backbone for the chemistry leading to the formation of several complex molecular species in space. A comprehensive understanding of the mechanisms involved in these reactions in the ISM necessitates an accurate knowledge of the rate coefficients at the relevant temperatures (10 to 100 K). We present measurements of the rate coefficients for two key reactions below 100 K, which, in both cases, are significantly higher than the values used in astronomical models thus far. The experimental rate coefficients show excellent agreement with dedicated theoretical calculations using a novel ring-polymer molecular dynamics approach that offers a first-principles treatment of low-temperature barrierless gas-phase reactions, which are prevalent in interstellar chemical networks.