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While the dissociative recombination (DR) of ground-state molecular ions with low-energy free electrons is generally known to be exothermic, it has been predicted to be endothermic for a class of transition-metal oxide ions. To understand this unusual case, the electron recombination of titanium oxide ions (TiO+) with electrons has been experimentally investigated using the Cryogenic Storage Ring. In its low radiation field, the TiO+ ions relax internally to low rotational excitation (≲100 K). Under controlled collision energies down to ∼ 2 meV within the merged electron and ion beam configuration, fragment imaging has been applied to determine the kinetic energy released to Ti and O neutral reaction products. Detailed analysis of the fragment imaging data considering the reactant and product excitation channels reveals an endothermicity for the TiO+ dissociative electron recombination of (+4 ± 10) meV. This result improves the accuracy of the energy balance by a factor of 7 compared to that found indirectly from hitherto known molecular properties. Conversely, the present endothermicity yields improved dissociation energy values for D0(TiO) = (6.824 ± 0.010) eV and D0(TiO+) = (6.832 ± 0.010) eV. All thermochemistry values were compared to new coupled-cluster calculations and found to be in good agreement. Moreover, absolute rate coefficients for the electron recombination of rotationally relaxed ions have been measured, yielding an upper limit of 1 × 10−7 cm3 s−1 for typical conditions of cold astrophysical media. Strong variation of the DR rate with the TiO+ internal excitation is predicted. Furthermore, potential energy curves for TiO+ and TiO have been calculated using a multi-reference configuration interaction method to constrain quantum-dynamical paths driving the observed TiO+ electron recombination. [ABSTRACT FROM AUTHOR]

Recombination of N2H+ ions with electrons was studied using a stationary afterglow with a cavity ring-down spectrometer. We probed in situ the time evolutions of number densities of different rotational and vibrational states of recombining N2H+ ions and determined the thermal recombination rate coefficients for N2H+ in the temperature range of 80–350 K. The newly calculated vibrational transition moments of N2H+ are used to explain the different values of recombination rate coefficients obtained in some of the previous studies. No statistically significant dependence of the measured recombination rate coefficient on the buffer gas number density was observed. [ABSTRACT FROM AUTHOR]

Rate coefficients for nuclear spin state-specific recombination of H3+ ions with thermal electrons were measured using FALP and SA techniques at temperatures 77–300 K. For this purpose H2 gas with both thermal and enriched population of the para nuclear spin configuration was used. Measurements have shown that at 77 K para-H3+ exhibits five times higher binary recombination rate coefficient than ortho-H3+: (1.5 ± 0.4) × 10−7 vs. (3 ± 2) × 10−8 cm3s−1.

Detailed measurements employing a combination of a cryogenic flowing afterglow with Langmuir probe (Cryo-FALP II) and a stationary afterglow with near-infrared absorption spectroscopy (SACRDS) show that binary electron recombination of para-H+3 and ortho-H+3 ions occurs with significantly different rate coefficients, pabin and oabin, especially at very lowtemperatures. The measurements cover temperatures from 60Kto 300 K. At the lowest temperature of 60 K, recombination of para-H+3 is at least three times faster than that of ortho-H+3 (pabin = (1.8 ± 0.4) × 10-7 cm³ s-1 vs. oabin = (0+5-0) × 10-8 cm³ s-1). [ABSTRACT FROM AUTHOR]

We present studies on the thermalisation of H3+ ions in a cold He/Ar/H2 plasma at temperatures 30–70 K. We show that we are able to generate a rotationally thermalised H3+ ensemble with a population of rotational and nuclear spin states corresponding to a particular ion translational temperature. By varying the para-H2 fraction used in the experiment we are able to produce para-H3+ ions with fractional populations higher than those corresponding to thermodynamic values. At 35 K, only the lowest rotational states of para and ortho H3+ are populated. This is the first step towards experimental studies of electron–molecular ion recombination processes with precisely specified quantum states at astrophysically relevant temperatures. [ABSTRACT FROM AUTHOR]

The recombination of deuterated trihydrogen cations with electrons has been studied in afterglow plasmas containing mixtures of helium, argon, hydrogen and deuterium. By monitoring the fractional abundances of H3+, H2D+, HD2+ and D3+ as a function of the [D2]/[H2] ratio using infrared absorption observed in a cavity ring down absorption spectrometer (CRDS), it was possible to deduce effective recombination rate coefficients for H2D+ and HD2+ ions at a temperature of 80 K. From pressure dependences of the measured effective recombination rate coefficients the binary and the ternary recombination rate coefficients for both ions have been determined. The inferred binary and ternary recombination rate coefficients are: αbinH2D(80 K) = (7.1 ± 4.2) × 10−8 cm3 s−1, αbinHD2(80 K) = (8.7 ± 2.5) × 10−8 cm3 s−1, KH2D(80 K) = (1.1 ± 0.6) × 10−25 cm6 s−1 and KHD2(80 K) = (1.5 ± 0.4) × 10−25 cm6 s−1. [ABSTRACT FROM AUTHOR]

Stationary afterglow (SA) experiments with cavity ring down absorption spectrometer (cw-CRDS) have been used to study recombination of H+3 ions with electrons. To characterize the plasma during the afterglow we monitored the time evolution of density of He2 excited dimers (a³Σ+u) in plasmas in pure helium and in helium with small admixture of Ar and H2. By monitoring the plasma decay and its dependence on [H2] and [Ar] in the afterglow in pure He and in He/Ar/H2 mixture we estimated the rate of plasma thermalization in the temperature range of 80-300 K. The inferred deexcitation rate coefficients for reaction of helium metastable atoms with H2 were (0.9 ± 0.3)×10-10 cm³ s-1, (1.9 ± 0.2)×10-10 cm³ s-1 and (2.7 ± 0.2) × 10-10 cm³ s-1 at 80 K, 140 K and 300 K, respectively. The effective recombination rate coefficients for H+3 were evaluated from the decay of the electron number density. We propose the lower estimate for the saturation of the effective recombination rate coefficient in H+3 and D+3 dominated plasma. [ABSTRACT FROM AUTHOR]

The epoch of first star formation in the early Universe was dominated by simple atomic and molecular species consisting mainly of two elements: hydrogen and helium. Gaining insight into this constitutive era requires a thorough understanding of molecular reactivity under primordial conditions. We used a cryogenic ion storage ring combined with a merged electron beam to measure state-specific rate coefficients of dissociative recombination, a process by which electrons destroy molecular ions. We found a pronounced decrease of the electron recombination rates for the lowest rotational states of the helium hydride ion (HeH+), compared with previous measurements at room temperature. The reduced destruction of cold HeH+ translates into an enhanced abundance of this primordial molecule at redshifts of first star and galaxy formation. [ABSTRACT FROM AUTHOR]

Recombination of N 2 H + ions with electrons was studied using a stationary afterglow with a cavity ring-down spectrometer. We probed in situ the time evolutions of number densities of different rotational and vibrational states of recombining N 2 H + ions and determined the thermal recombination rate coefficients for N 2 H + in the temperature range of 80-350 K. The newly calculated vibrational transition moments of N 2 H + are used to explain the different values of recombination rate coefficients obtained in some of the previous studies. No statistically significant dependence of the measured recombination rate coefficient on the buffer gas number density was observed.

We present studies on the thermalisation of H3+ ions in a cold He/Ar/H2 plasma at temperatures 30-70 K. We show that we are able to generate a rotationally thermalised H3+ ensemble with a population of rotational and nuclear spin states corresponding to a particular ion translational temperature. By varying the para-H2 fraction used in the experiment we are able to produce para-H3+ ions with fractional populations higher than those corresponding to thermodynamic values. At 35 K, only the lowest rotational states of para and ortho H3+ are populated. This is the first step towards experimental studies of electron-molecular ion recombination processes with precisely specified quantum states at astrophysically relevant temperatures.