Recombination of vibrationally cold N2+ ions with electrons.

Recombination of vibrationally cold N2+ ions with electrons was studied in the temperature range of 140-250 K. A cryogenic stationary afterglow apparatus equipped with cavity ring-down spectrometer and microwave diagnostics was utilized to probe in situ the time evolutions of number densities of particular rotational and vibrational states of N2+ ions and of electrons. The obtained value of the recombination rate coefficient for the recombination of the vibrational ground state of N2+ with electrons is αv=0 = (2.95 ± 0.50) × 10-7(300/T)(0.28±0.07) cm3 s-1, while that for the first vibrationally excited state was inferred as αv=1 = (4 ± 4) × 10-8 cm3 s-1 at 250 K.

The reaction of O+(4S) ions with H2, HD, and D2 at low temperatures: Experimental study of the isotope effect.

The reactions of the O+ ions in the 4S electronic ground state with D2 and HD were studied in a cryogenic 22-pole radio-frequency ion trap in the temperature range of 15 K-300 K. The obtained reaction rate coefficients for both reactions are, considering the experimental errors, nearly independent of temperature and close to the values of the corresponding Langevin collisional reaction rate coefficients. The obtained branching ratios for the production of OH+ and OD+ in the reaction of O+(4S) with HD do not change significantly with temperature and are consistent with the results obtained at higher collisional energies by other groups. Particular attention was given to ensure that the O+ ions in the trap are in the ground electronic state.

Stationary afterglow apparatus with CRDS for study of processes in plasmas from 300 K down to 30 K.

A cryogenic stationary afterglow apparatus equipped with a near-infrared cavity-ring-down-spectrometer (Cryo-SA-CRDS) for studies of electron-ion recombination processes in the plasma at temperatures 30-300 K has been designed, constructed, tested, and put into operation. The plasma is generated in a sapphire discharge tube that is contained in a microwave cavity. The cavity and the tube are attached to the second stage of the cold head of the cryocooler system, and they are inserted to an UHV chamber with mirrors for CRDS and vacuum windows on both ends of the tube. The temperature of the discharge tube can be made as low as 25 K. In initial test measurements, the discharge was ignited in He/Ar/H2 or He/H2 gas mixtures and the density of H3+ ions and their kinetic and rotational temperatures were measured during the discharge and afterglow. From the measured decrease in the ion density, during the afterglow, effective recombination rate coefficients were determined. Plasma relaxation was studied in He/Ar gas mixtures by monitoring the presence of highly excited argon atoms. The spectroscopic measurements demonstrated that the kinetic temperature of the ions is equal to the gas temperature and that it can be varied from 300 K down to 30 K.

Interaction of O(-) and H2 at low temperatures.

Reactive collisions between O(-) and H2 have been studied experimentally at temperatures ranging from 10 K to 300 K using a cryogenic radiofrequency 22-pole ion trap. The rate coefficients for associative detachment, leading to H2O + e(-), increase with decreasing temperature and reach a flat maximum of 1.8 × 10(-9) cm(3) s(-1) at temperatures between 20 K and 80 K. There, the overall reaction probability is in good agreement with a capture model indicating efficient non-adiabatic couplings between the entrance potential energy surfaces. Classical trajectory calculations on newly calculated potential energy surfaces as well as the topology of the conical intersection seam leading to the neutral surface corroborate this. The formation of OH(-) + H via hydrogen transfer, although occurring with a probability of a few percent only (about 5 × 10(-11) cm(3) s(-1) at temperatures 10-300 K), indicates that there are reaction paths, where electron detachment is avoided.

State specific stabilization of H+ + H2(j) collision complexes.

Stabilization of H3(+) collision complexes has been studied at nominal temperatures between 11 and 33 K using a 22-pole radio frequency (rf) ion trap. Apparent binary rate coefficients, k(*) = kr + k3[H2], have been measured for para- and normal-hydrogen at number densities between some 10(11) and 10(14) cm(-3). The state specific rate coefficients extracted for radiative stabilization, kr(T;j), are all below 2 × 10(-16) cm(3) s(-1). There is a slight tendency to decrease with increasing temperature. In contrast to simple expectations, kr(11 K;j) is for j = 0 a factor of 2 smaller than for j = 1. The ternary rate coefficients for p-H2 show a rather steep T-dependence; however, they are increasing with temperature. The state specific ternary rate coefficients, k3(T;j), measured for j = 0 and derived for j = 1 from measurements with n-H2, differ by an order of magnitude. Most of these surprising observations are in disagreement with predictions from standard association models, which are based on statistical assumptions and the separation of complex formation and competition between stabilization and decay. Most probably, the unexpected collision dynamics are due to the fact that, at the low translational energies of the present experiment, only a small number of partial waves participate. This should make exact quantum mechanical calculations of kr feasible. More complex is three-body stabilization, because it occurs on the H5(+) potential energy surface.

Ternary recombination of H3(+) and D3(+) with electrons in He-H2 (D2) plasmas at temperatures from 50 to 300 k.

We present results of plasma afterglow experiments on ternary electron-ion recombination rate coefficients of H3(+) and D3(+) ions at temperatures from 50 to 300 K and compare them to possible three-body reaction mechanisms. Resonant electron capture into H3* Rydberg states is likely to be the first step in the ternary recombination, rather than third-body-assisted capture. Subsequent interactions of the Rydberg molecules with ambient neutral and charged particles provide the rate-limiting step that completes the recombination. A semiquantitative model is proposed that reconciles several previously discrepant experimental observations. A rigorous treatment of the problem will require additional theoretical work and experimental investigations.

Binary recombination of para- and ortho-H3+ with electrons at low temperatures.

Results of an experimental study of binary recombination of para- and ortho-H(3)(+) ions with electrons are presented. Near-infrared cavity-ring-down absorption spectroscopy was used to probe the lowest rotational states of H(3)(+) ions in the temperature range of 77-200 K in an H(3)(+)-dominated afterglow plasma. By changing the para/ortho abundance ratio, we were able to obtain the binary recombination rate coefficients for pure and para-H(3)(+) and ortho-H(3)(+). The results are in good agreement with previous theoretical predictions.

Nuclear spin effect on recombination of H3⁺ ions with electrons at 77 K.

Utilizing different ratios of para to ortho H2 in normal and para enriched hydrogen, we varied the population of para-H3⁺ in an H3⁺ dominated plasma at 77 K. Absorption spectroscopy was used to measure the densities of the two lowest rotational states of H3⁺. Monitoring plasma decays at different populations of para-H3⁺ allowed us to determine the rate coefficients for binary recombination of para-H3⁺ and ortho-H3⁺ ions: (p)α(bin)(77 K) = (1.9 ± 0.4) × 10⁻7 cm³ s⁻¹ and (o)α(bin)(77 K) = (0.2 ± 0.2) × 10⁻7 cm³ s⁻¹.

Temperature dependence of binary and ternary recombination of D3+ ions with electrons.

Flowing and stationary afterglow experiments were performed to study the recombination of D(3)(+) ions with electrons at temperatures from 77 to 300 K. A linear dependence of apparent (effective) binary recombination rate coefficients on the pressure of the helium buffer gas was observed. Binary (D(3)(+)+e(-)) and ternary (D(3)(+)+e(-)+He) recombination rate coefficients were derived. The obtained binary rate coefficient agrees with recent theoretical values for dissociative recombination of D(3)(+). We describe the observed ternary process by a mechanism with two rate determining steps. In the first step, a rotationally excited long-lived neutral D(3)* is formed in D(3)(+)-e(-) collisions. As the second step, the D(3)* collides with a helium atom that prevents autoionization of D(3)*. We calculate lifetimes of D(3)* formed from ortho-, para-, or metastates of D(3)(+) and use the lifetimes to calculate ternary recombination rate coefficients.

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.

Dynamical constraints and nuclear spin caused restrictions in HmD+ collision systems.

This contribution summarizes a variety of results and ongoing activities, which contribute to our understanding of inelastic and reactive collisions involving hydrogen ions. In an overview of our present theoretical knowledge of various HmD+ collision systems (m + n < or = 5), it is emphasized that although the required potential energy surfaces are well characterized, no detailed treatments of the collision dynamics are available to date, especially at the low energies required for astrochemistry. Instead of treating state-to-state dynamics with state of the art methods, predictions are still based on: (i) simple thermodynamical arguments, (ii) crude reaction models such as H atom exchange or proton jump, or (iii) statistical considerations used for describing processes proceeding via long-lived or strongly interacting collision complexes. A central problem is to properly account for the consequences of the fact that H and D are fermions and bosons, respectively. In the experimental and results sections, it is emphasized that although a variety of innovative techniques are available and have been used for measuring rate coefficients, cross-sections or state-to-state transition probabilities, the definitive experiments are still pending. In the centre of this contribution are our activities on various m + n = 5 systems. We report a few selected additional results for collisions of hydrogen ions with p-H2, o-H2, HD, D2 or well-defined mixtures of these neutrals. Most of the recent experiments are based on temperature variable multipole ion traps and their combination with pulsed gas inlets, molecular beams, laser probing or electron beams. Based on the state-specific model calculations, it is concluded that for completely understanding the gas phase formation and destruction of HmDn+ in a trap, an in situ characterization of all the experimental parameters is required with unprecedented accuracy. Finally, the need to understand the hydrogen chemistry relevant for dense pre-stellar cores is discussed.

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).

Recombination of D3+ ions in the afterglow of a He-Ar- D2 plasma.

We report measurements of the rate coefficient alpha for recombination of D3+ with electrons in a He-Ar-D2 plasma. The observed rate coefficient is dependent on the deuterium number density indicating that third-body assisted recombination is efficient and significantly contributes to recombination. When the deuterium number density is decreased to 7x10(10) cm(-3), the rate coefficient also decreases to alpha approximately 6x10(-9) cm3 x s(-1). These data indicate that the binary dissociative recombination of D3+ is very slow with alphaDR<6x10(-9) cm3 x s(-1). The observation of a deionization process proceeding via formation of D5+ is also reported.