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.

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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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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.

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Recombination of D(3)(+) ions with electrons at low temperatures (80-130 K) was studied using spectroscopic determination of D(3)(+) ions density in afterglow plasmas. The use of cavity ring-down absorption spectroscopy enabled an in situ determination of the abundances of the ions in plasma and the translational and the rotational temperatures of the recombining ions. Two near infrared transitions at (5792.70 ± 0.01) cm(-1) and at (5793.90 ± 0.01) cm(-1) were used to probe the number densities of the lowest ortho state and of one higher lying rotational state of the vibrational ground state of D(3)(+) ion. The results show that D(3)(+) recombination with electrons consists of the binary and the third-body (helium) assisted process. The obtained binary recombination rate coefficients are in agreement with a recent theoretical prediction for electron-ion plasma in thermodynamic equilibrium with α(bin)(80 K) = (9.2 ± 2.0) × 10(-8) cm(3) s(-1). The measured helium assisted ternary rate coefficients K(He) are in agreement with our previously measured flowing afterglow data giving a value of K(He)(80 K) = (1.2 ± 0.3) × 10(-25) cm(6) s(-1).