The destruction of CH + ions in collisions with H atoms has been studied in a temperature-variable 22 pole ion trap (22PT) combined with a cold effusive H-atom beam. The stored ions are relaxed to temperatures of T 22PT 12 K. The hydrogen atoms, produced in a radio frequency discharge, are slowed down to various temperatures of T ACC 7 K. They are formed into an effusive beam. The effective density of the hydrogen atoms in the trap as well as the H 2 background are determined in situ using chemical probing with CO 2 +. The experimental arrangement allows us not only to measure thermal rate coefficients (T 22PT = T ACC), but also to extract state-specific rate coefficients k(J,T t) at selected translational temperatures T t and for the CH + rotational states J = 0, 1, and 2. The measured thermal rate coefficients have a maximum at 60 K, k = (1.2 ± 0.5)×10 −9 cm 3 s −1. Toward higher temperatures, they fall off in accordance with previous measurements and the trend predicted by phase space theory. Toward lower temperatures, the rate coefficients decrease significantly, especially if the rotation of the ions is cooled. At the coldest conditions achieved (beam: 7.3 K; trap: 12.2 K), a value as low as (5 ± 4) × 10 −11 cm 3 s −1 has been measured. This leads to the conclusion that non-rotating CH + is protected against attacks of H atoms. This surprising result is not yet understood. It is most probably due to quantum-dynamical effects already occurring at large distances.

We study binary and the recently discovered process of ternary He-assisted recombination of H 3 + ions with electrons in a low-temperature afterglow plasma. The experiments are carried out over a broad range of pressures and temperatures of an afterglow plasma in a helium buffer gas. Binary and He-assisted ternary recombination are observed and the corresponding recombination rate coefficients are extracted for temperatures from 77 to 330 K. We describe the observed ternary recombination as a two-step mechanism: first, a rotationally excited long-lived neutral molecule H 3 ‫ء‬ is formed in electron-H 3 + collisions. Second, the H 3 ‫ء‬ molecule collides with a helium atom that leads to the formation of a very long-lived Rydberg state with high orbital momentum. We present calculations of the lifetimes of H 3 ‫ء‬ and of the ternary recombination rate coefficients for para-and ortho-H 3 + . The calculations show a large difference between the ternary recombination rate coefficients of ortho-and para-H 3 + at temperatures below 300 K. The measured binary and ternary rate coefficients are in reasonable agreement with the calculated values.

Measurements in H(3)(+) afterglow plasmas with spectroscopically determined relative abundances of H(3)(+) ions in the para-nuclear and ortho-nuclear spin states provide clear evidence that at low temperatures (77-200 K) para-H(3)(+) ions recombine significantly faster with electrons than ions in the ortho state, in agreement with a recent theoretical prediction. The cavity ring-down absorption spectroscopy used here provides an in situ determination of the para/ortho abundance ratio and yields additional information on the translational and rotational temperatures of the recombining ions. The results show that H(3)(+) recombination with electrons occurs by both binary recombination and third-body (helium) assisted recombination, and that both the two-body and three-body rate coefficients depend on the nuclear spin states. Electron-stabilized (collisional-radiative) recombination appears to make only a small contribution.

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.

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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.

We have applied a continuous-wave near-infrared cavity ring-down spectroscopy method to study the parameters of a H + 3 -dominated plasma at temperatures in the range 77-200 K. We monitor populations of three rotational states of the ground vibrational state corresponding to para and ortho nuclear spin states in the discharge and the afterglow plasma in time and conclude that abundances of para and ortho states and rotational temperatures are well defined and stable. The non-trivial dependence of a relative population of para-H + 3 on a relative population of para-H 2 in a source H 2 gas is described. The results described in this paper are valuable for studies of state-selective dissociative recombination of H + 3 ions with electrons in the afterglow plasma and for the design of sources of H + 3 ions in a specific nuclear spin state.

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.