RESUMO
We present a merged-beams study of reactions between HD^{+} ions, stored in the Cryogenic Storage Ring (CSR), and laser-produced ground-term C atoms. The molecular ions are stored for up to 20 s in the extreme vacuum of the CSR, where they have time to relax radiatively until they reach their vibrational ground state (within 0.5 s of storage) and rotational states with J≤3 (after 5 s). We combine our experimental studies with quasiclassical trajectory calculations based on two reactive potential energy surfaces. In contrast to previous studies with internally excited H_{2}^{+} and D_{2}^{+} ions, our results reveal a pronounced isotope effect, favoring the production of CH^{+} over CD^{+} across all collision energies, and a significant increase in the absolute rate coefficient of the reaction. Our experimental results agree well with our theoretical calculations for vibrationally relaxed HD^{+} ions in their lowest rotational states.
RESUMO
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 (â²100 K). Under controlled collision energies down to â¼2 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.
RESUMO
We present state-selected measurements of rotational cooling and excitation rates of CH^{+} molecular ions by inelastic electron collisions. The experiments are carried out at a cryogenic storage ring, making use of a monoenergetic electron beam at matched velocity in combination with state-sensitive laser dissociation of the CH^{+} ions for simultaneous monitoring of the rotational level populations. Employing storage times of up to 600 s, we create conditions where electron-induced cooling to the J=0 ground state dominates over radiative relaxation, allowing for the experimental determination of inelastic electron collision rates to benchmark state-of-the-art theoretical calculations. On a broader scale, our experiments pave the way to probe inelastic electron collisions for a variety of molecular ions relevant in various plasma environments.
RESUMO
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.
RESUMO
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.
RESUMO
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) cm(3) s(-1), αbinHD2(80 K) = (8.7 ± 2.5) × 10(-8) cm(3) s(-1), KH2D(80 K) = (1.1 ± 0.6) × 10(-25) cm(6) s(-1) and KHD2(80 K) = (1.5 ± 0.4) × 10(-25) cm(6) s(-1).
RESUMO
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 (SA-CRDS) show that binary electron recombination of para-H3(+) and ortho-H3(+) ions occurs with significantly different rate coefficients, (p)αbin and (o)αbin, especially at very low temperatures. The measurements cover temperatures from 60 K to 300 K. At the lowest temperature of 60 K, recombination of para-H3(+) is at least three times faster than that of ortho-H3(+) ((p)αbin=(1.8±0.4)×10(-7) cm(3) s(-1) vs. (o)αbin=(0-0 (+5))×10(-8) cm(3) s(-1)).
RESUMO
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 Δm/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%.
RESUMO
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.