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.

Dynamics of the isotope exchange reaction of D with H3 +, H2D+, and D2H.

We have measured the merged-beams rate coefficient for the titular isotope exchange reactions as a function of the relative collision energy in the range of ∼3 meV-10 eV. The results appear to scale with the number of available sites for deuteration. We have performed extensive theoretical calculations to characterize the zero-point energy corrected reaction path. Vibrationally adiabatic minimum energy paths were obtained using a combination of unrestricted quadratic configuration interaction of single and double excitations and internally contracted multireference configuration interaction calculations. The resulting barrier height, ranging from 68 meV to 89 meV, together with the various asymptotes that may be reached in the collision, was used in a classical over-the-barrier model. All competing endoergic reaction channels were taken into account using a flux reduction factor. This model reproduces all three experimental sets quite satisfactorily. In order to generate thermal rate coefficients down to 10 K, the internal excitation energy distribution of each H3 + isotopologue is evaluated level by level using available line lists and accurate spectroscopic parameters. Tunneling is accounted for by a direct inclusion of the exact quantum tunneling probability in the evaluation of the cross section. We derive a thermal rate coefficient of <1×10-12 cm3 s-1 for temperatures below 44 K, 86 K, and 139 K for the reaction of D with H3 +, H2D+, and D2H+, respectively, with tunneling effects included. The derived thermal rate coefficients exceed the ring polymer molecular dynamics prediction of Bulut et al. [J. Phys. Chem. A 123, 8766 (2019)] at all temperatures.

Design and characteristics of a cavity-enhanced Fourier-transform spectrometer based on a supercontinuum source.

We report the in-house fabrication of a high-resolution Fourier-transform spectrometer (FTS) for the spectroscopy of molecules in the gas phase at resolutions down to 0.002 cm-1 working in the spectral range from 5880 cm-1 (1.7 µm) to 15 380 cm-1 (650 nm). The FTS employs a supercontinuum as a broadband light source and a He:Ne laser with a homemade frequency-stabilization scheme as the spatial reference for the sampling of the interferogram on a constant optical path difference (OPD) grid. The sampling of the two lasers is performed at constant time intervals, and the resampling process is performed at the software level. The resampling of the interferogram on a constant OPD grid relies on cubic approximations of the He:Ne interference pattern to determine its zero-crossings. The use of an invariant in the sampling process allows us to perform on-the-fly data treatment. Both the hardware aspect and the data processing are described with, in each case, an original approach. We also report the successful coupling of the FTS with a high finesse optical cavity with effective mirror reflectivities of 99.76%, allowing us to reach sensitivities down to 6.5 × 10-8 cm-1 with a root-mean-square accuracy of 0.0017 cm-1 on the position of the Doppler-broadened transitions with a mean transition width of 0.046 cm-1 for spectra recorded at a spectral resolution of 0.015 cm-1. The sensitivity of the instrument per spectral element, once normalized, represents the best sensitivity reported in the literature for Fourier-transform incoherent broadband cavity-enhanced absorption spectroscopy with a supercontinuum light source.

Photodissociation as a probe of the H3+ avoided crossing seam.

Experiments are conducted to investigate the role of the avoided crossing seam in the photodissociation of H3+. Three-dimensional imaging of dissociation products is used to determine the kinetic energy release and branching ratio among the fragmentation channels. Vibrational distributions are measured by dissociative charge transfer of H2+ products. It is found that the photodissociation of hot H3+ in the near-ultraviolet produces cold H2+, but hot H2. Modelling the wavepacket dynamics along the repulsive potential energy surface accounts for the repopulation of the ground potential energy surface. The role of the avoided crossing seam is emphasized and its importance for the astrophysically relevant charge transfer reactions underlined. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H3+, H5+ and beyond'.

Mutual Neutralization of O

We have measured total absolute cross sections for the mutual neutralization (MN) of O^{-} with O^{+} and N^{+}. A fine resolution (of about 50 meV) in the kinetic energy spectra of the product neutral atoms allows unique identification of the atomic states participating in the mutual neutralization process. Cross sections and branching ratios have also been calculated down to 1 meV center-of-mass collision energy for these two systems, with a multichannel Landau-Zener model and an asymptotic method for the ionic-covalent coupling matrix elements. The importance of two-electron processes in one-electron transfer is demonstrated by the dominant contribution of a core-excited configuration of the nitrogen atom in N^{+}+O^{-} collisions. This effect is partially accounted for by introducing configuration mixing in the evaluation of coupling matrix elements.

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.

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.

Background elimination and interferometric capability in optical coherence tomography by a nonlinear optical gating based on type-II second-harmonic generation.

A novel method that uses nonlinear optical gating to control background illumination in optical coherence tomography is presented. With this method, the user can adjust the amount of undesired backscattering or eliminate it completely, which enables dark-field measurements. The interferometric capability of the method in a nonlinear optical regime is demonstrated with the coupling of three overlapping input waves to yield Fizeau fringes. The measurement of a 265 nm step is performed to validate this method, which was originally conceived for 3D MEMS characterization.

A zero dead-time multi-particle time and position sensitive detector based on correlation between brightness and amplitude.

A new multi-particle time and position sensitive detector using only a set of microchannel plates, a waveform digitizer, a phosphor screen, and a CMOS camera is described. The assignment of the timing information, as taken from the microchannel plates by fast digitizing, to the positions, as recorded by the camera, is based on the COrrelation between the BRightness of the phosphor screen spots, defined as their integrated intensity and the Amplitude of the electrical signals (COBRA). Tests performed by observing the dissociation of HeH, the fragmentation of H3 into two or three fragments, and the photo-double-ionization of Xenon atoms are presented, which illustrate the performances of the COBRA detection scheme.

New light shed on charge transfer in fundamental H+ + H2 collisions.

There is no consensus on the magnitude and shape of the charge transfer cross section in low-energy H+ + H2 collisions, in spite of the fundamental importance of these collisions. Experiments have thus been carried out in the energy range 15≤E≤5000 eV. The measurements invalidate previous recommended data for E≤200 eV and confirm the existence of a local maximum around 45 eV, which was predicted theoretically. Additionally, vibrationally resolved cross sections allow us to investigate the evolution of the underlying charge transfer mechanism as a function of E.

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 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.

Ultraviolet and visible light photodissociation of H3+ in an ion storage ring.

Ultraviolet and visible photodissociation of a vibrationally excited H(3)(+) ion beam, as produced by standard ion sources, was successfully implemented in an ion storage ring with the aim of investigating the decay of the excited molecular levels. A collinear beams configuration was used to measure the photodissociation of H(3)(+) into H(2)(+) + H fragments by transitions into the first excited singlet state with 266 and 532 nm laser beams. A clear signal could be observed up to 5 ms of storage, indicating that enough highly excited rovibrational states survive on the millisecond time scale of the experiment. The decay into H(2)(+) + H shows an effective time constant between about 1 and 1.5 ms. The initial photodissociating states are estimated to lie roughly 1 eV below the dissociation limit of 4.4 eV. The expected low population of these levels gives rise to an effective cross section of several 10(-20) cm(2) for ultraviolet and some 10(-21) cm(2) for visible light. For using multistep resonant dissociation schemes to monitor rotational populations of cold H(3)(+) in low-density environments, these measurements open promising perspectives.

Laser-intensity dependent vibrational excitation and alignment of molecular ions in the ultrafast multiphoton regime.

H2 molecules were ionized in the ultrafast (approximately 150 fs) multiphoton regime (263 nm, approximately 10(13) W cm(-2)). Earlier experiments investigated the kinetic energies of electrons or ions only. Using a unique experiment, we show that the vibrational excitation of molecular ions contains essential information about the dynamics of the process. In addition, we prove some earlier interpretations wrong. A realistic model based on vibronically excited intermediates, Stark shifting into resonance, reproduces the measurements, demonstrating that resonances continue to be important in the femtosecond regime. This eventually enables ultrafast control of the vibrational excitation of molecular ions, which is relevant to the whole field of molecular physics and physical chemistry.

Reactive collisions between CH+ and O-.

Integral cross sections were measured for two reactions occurring in CH+ + O- collisions: the formation of the carbon monoxide cation CO+ via a reactive ionization process and the formation of the (iso)formyl cation HCO+ (HOC+) via the associative ionization process. Both carbon monoxide and formyl cations are present in the interstellar medium, the latter one being quite abundant in dense clouds. Provided the oxygen anion would also be present in the interstellar environment, the large efficiency of the two reactive processes reported here would justify their inclusion in astrochemical models. The whole set of data was obtained by means of a merged-beam setup operating with keV beams.

Intense-laser-field ionization of molecular hydrogen in the tunneling regime and its effect on the vibrational excitation of H2+.

H2 molecules were ionized by Ti:sapphire (45 fs, 800 nm) and Nd-doped yttrium aluminum garnet lasers (6 ns, 1064 nm). The relative populations of the vibrational levels of the H+2 ions were determined and found to be concentrated in the lowest vibrational levels. Tunneling ionization calculations with exact field-modified potential curves reproduce the experimental results. The reason for the departure from conventional Franck-Condon-like distributions is the rapid variation of the ionization rate with internuclear distance.