An ion-atom merged beams setup at the Cryogenic Storage Ring.

We describe a merged beams experiment to study ion-neutral collisions at the Cryogenic Storage Ring of the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. We produce fast beams of neutral atoms in their ground term at kinetic energies between 10 and 300 keV by laser photodetachment of negative ions. The neutral atoms are injected along one of the straight sections of the storage ring, where they can react with stored molecular ions. Several dedicated detectors have been installed to detect charged reaction products of various product-to-reactant mass ranges. The relative collision energy can be tuned by changing the kinetic energy of the neutral beam in an independent drift tube. We give a detailed description of the setup and its capabilities, and present proof-of-principle measurements on the reaction of neutral C atoms with D2 + ions.

Astrochemical studies at the Cryogenic Storage Ring.

The new Cryogenic Storage Ring at the Max Planck Institute for Nuclear Physics (Heidelberg, Germany) has recently become operational. One of the main research areas foreseen for this unique facility is astrochemical studies with cold molecular ions. The spontaneous radiative cooling of the prototype interstellar molecule CH+ to its lowest rotational states has been demonstrated by photodissociation spectroscopy, paving the way for experiments under true interstellar conditions. To this end, a low-energy electron cooler and a neutral atom beam set-up for merged beams studies have been constructed. These experiments have the potential to provide energy-resolved rate coefficients for fundamental astrochemical processes involving state-selected molecular ions. The main target reactions include some of the key processes of interstellar chemistry, such as the electron recombination of H3+, charge exchange between H2+ and H, or the formation of CH+ in collisions of triatomic hydrogen ions and C atoms. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H3+, H5+ and beyond'.

Radiative Rotational Lifetimes and State-Resolved Relative Detachment Cross Sections from Photodetachment Thermometry of Molecular Anions in a Cryogenic Storage Ring.

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 min 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.

The cryogenic storage ring CSR.

An electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.5 ± 1) K inside the ring, storage time constants of several minutes up to almost an hour were observed for atomic and molecular, anion and cation beams at an energy of 60 keV. The ion-beam intensity, energy-dependent closed-orbit shifts (dispersion), and the focusing properties of the machine were studied by a system of capacitive pickups. The Schottky-noise spectrum of the stored ions revealed a broadening of the momentum distribution on a time scale of 1000 s. Photodetachment of stored anions was used in the beam lifetime measurements. The detachment rate by anion collisions with residual-gas molecules was found to be extremely low. A residual-gas density below 140 cm(-3) is derived, equivalent to a room-temperature pressure below 10(-14) mbar. Fast atomic, molecular, and cluster ion beams stored for long periods of time in a cryogenic environment will allow experiments on collision- and radiation-induced fragmentation processes of ions in known internal quantum states with merged and crossed photon and particle beams.

Photodissociation of an Internally Cold Beam of CH

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.

Generation of neutral atomic beams utilizing photodetachment by high power diode laser stacks.

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 ∼7.4% for H(-) at a beam energy of 10 keV and ∼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.

Structure and stability of the negative hydrogen molecular ion.

We present the results of a Coulomb explosion experiment that allows for the imaging of the rovibrational wave function of the metastable H2- ion. Our measurements confirm the predicted large internuclear separation of 6 a.u., and they show that the ion decays by autodetachment rather than by spontaneous dissociation. Imaging of the resulting H2 products reveals a large angular momentum of J = 25 ± 2, quantifying the rotation that leads to the metastability of this most fundamental molecular anion.

Experimental results for H2 formation from H- and H and implications for first star formation.

During the epoch of first star formation, molecular hydrogen (H2) generated via associative detachment (AD) of H- and H is believed to have been the main coolant of primordial gas for temperatures below 10(4) kelvin. The uncertainty in the cross section for this reaction has limited our understanding of protogalaxy formation during this epoch and of the characteristic masses and cooling times for the first stars. We report precise energy-resolved measurements of the AD reaction, made with the use of a specially constructed merged-beams apparatus. Our results agreed well with the most recent theoretically calculated cross section, which we then used in cosmological simulations to demonstrate how the reduced AD uncertainty improves constraints of the predicted masses for Population III stars.

A simple double-focusing electrostatic ion beam deflector.

We have developed an electrostatic, double-focusing 90 degrees deflector for fast ion beams consisting of concentric cylindrical plates of differing heights. In contrast to standard cylindrical deflectors, our design allows for focusing of an incoming parallel beam not only in the plane of deflection but also in the orthogonal direction. The optical properties of our design resemble those of a spherical capacitor deflector while it is much easier and more cost effective to manufacture.

A novel merged beams apparatus to study anion-neutral reactions.

We have developed a novel laboratory instrument for studying gas phase, anion-neutral chemistry. To the best of our knowledge, this is the first such apparatus which uses fast merged beams to investigate anion-neutral chemical reactions. As proof-of-principle we have detected the associative detachment reaction H(-)+H-->H(2)+e(-). Here we describe the apparatus in detail and discuss related technical and experimental issues.

Rotational cooling of HD+ molecular ions by superelastic collisions with electrons.

Merging an HD+ beam with velocity matched electrons in a heavy ion storage ring we observed rapid cooling of the rotational excitations of the HD+ ions by superelastic collisions (SEC) with the electrons. The cooling process is well described using theoretical SEC rate coefficients obtained by combining the molecular R-matrix approach with the adiabatic nuclei rotation approximation. We verify the DeltaJ=-2 SEC rate coefficients, which are predicted to be dominant as opposed to the DeltaJ=-1 rates and to amount to (1-2)x10;{-6} cm;{3} s;{-1} for initial angular momentum states with J< or =7, to within 30%.

Effects of molecular rotation in low-energy electron collisions of H3+.

Measurements on the energetic structure of the dissociative recombination rate coefficient in the millielectronvolt range are described for H3+ ions produced in the lowest rotational levels by collisional cooling and stored as a fast beam in the magnetic storage ring TSR (Test Storage Ring). The observed resonant structure is consistent with that found previously at the storage ring facility CRYRING in Stockholm, Sweden; theoretical predictions yield good agreement on the overall size of the rate coefficient, but do not reproduce the detailed structure. First studies on the nuclear spin symmetry influencing the lowest level populations show a small effect different from the theoretical predictions. Heating processes in the residual gas and by collisions with energetic electrons, as well as cooling owing to interaction with cold electrons, were observed in long-time storage experiments, using the low-energy dissociative recombination rate coefficient as a probe, and their consistency with the recent cold H3+ measurements is discussed.

Action spectroscopy of H3+ and D2H+ using overtone excitation.

The H3+ ion and its deuterated isotopologues H2D+, D2H+ and D3+ play an important role in astrophysical and laboratory plasmas. The main challenge for understanding these ions and their interaction at low temperatures are state-specific experiments. This requires manipulation and a simple but efficient in situ characterization of their low-lying rotational states. In this contribution we report measurements of near infrared (NIR) absorption spectra. Required high sensitivity is achieved by combining liquid nitrogen cooled plasma with the technique of NIR cavity ringdown absorption spectroscopy. The measured transition frequencies are then used for exciting cold ions stored in a low-temperature 22-pole radiofrequency ion trap. Absorption of a photon by the stored ion is detected by using the laser-induced reactions technique. As a monitor reaction, the endothermic proton (or deuteron) transfer to Ar is used in our studies. Since the formed ArH+ (or ArD+) ions are detected with near unit efficiency, the stored ions can be characterized very efficiently, even if there are just a few of them.

High-resolution dissociative recombination of cold H3+and first evidence for nuclear spin effects.

The energy-resolved rate coefficient for the dissociative recombination (DR) of H(3)(+) with slow electrons has been measured by the storage-ring method using an ion beam produced from a radiofrequency multipole ion trap, employing buffer-gas cooling at 13 K. The electron energy spread of the merged-beams measurement is reduced to 500 microeV by using a cryogenic GaAs photocathode. This and a previous cold- measurement jointly confirm the capability of ion storage rings, with suitable ion sources, to store and investigate H(3)(+) in the two lowest, (J,G) = (1,1) and (1,0) rotational states prevailing also in cold interstellar matter. The use of para-H(2) in the ion source, expected to enhance para-H(3)(+) in the stored ion beam, is found to increase the DR rate coefficient at meV electron energies.

Action spectroscopy and temperature diagnostics of H+ 3 by chemical probing.

Infrared absorption spectroscopy of few hundred H+(3) ions trapped in a 22-pole ion trap is presented using chemical probing as a sensitive detection technique down to the single ion level. By exciting selected overtone transitions of the (v(1)=0,v(2) (l)=3(1))<--(0,0(0)) vibrational band using an external cavity diode laser an accurate diagnostics measurement of the effective translational and rotational temperatures of the trapped ions was performed. The absolute accuracy of the measured transition frequencies was improved by a factor of four compared to previous plasma spectroscopy measurements using velocity modulation [Ventrudo et al., J. Chem. Phys. 100, 6263 (1994)]. The observed buffer gas cooling conditions in the ion trap indicate how to cool trapped H+(3) ions into the lowest ortho and para rotational states. Future experiments will utilize such an internally cold ion ensemble for state-selected dissociative recombination experiments at the heavy ion storage ring Test Storage Ring (TSR).

Evidence for subthermal rotational populations in stored molecular ions through state-dependent dissociative recombination.

We demonstrate that the dissociative recombination of D2H+ with low-energy electrons depends on the rotational energy of the molecular ion such that highly excited ions have a larger rate coefficient than colder ones. Observations on an ion beam continuously interacting with electrons at low relative velocity indicate that excited rotational levels are preferentially depleted which, in competition with radiative heating due to blackbody radiation, provides an opportunity for controlling the rotational temperature of stored molecules.

Rate coefficients and final states for the dissociative recombination of LiH+.

The dissociative recombination of LiH+ ions with low-energy electrons is observed at a storage ring and the final states are analyzed using fragment imaging and field ionization techniques. The rate coefficient is found to be larger than its estimated value used in astrophysical models. Mostly the highest energetically possible Rydberg states of the lithium atom are populated by the reaction, indicating a common trend for molecular recombination via the noncrossing mode.

Two- and three-body kinematical correlation in the dissociative recombination of H(3)(+).

Fragmentation patterns for dissociative recombination of the triatomic hydrogen molecular ion H(3)(+) in the vibrational ground state have been measured using the storage ring technique and molecular fragment imaging. A broad distribution of vibrational states in the H(2) fragment after two-body dissociation and a large predominance of nearly linear momentum geometries after three-body dissociation are found. The fragmentation results are directly contrasted with Coulomb explosion imaging data on the initial H(3)(+) geometry, compared to existing wave-packet calculations, and considered in the light of a simple physical picture.