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.