H 3 + + H 2 isotopic system at low temperatures: Microcanonical model and experimental study

Abstract

State-to-state thermal rate coefficients for reactions of all H 3 + + H 2 isotopic variants are derived and compared to new experimental data. The theoretical data are also sought for astrochemical modeling of cold environments ( < 50 K ) . The rates are calculated on the basis of a microcanonical approach using the Langevin model and the conservation laws of mass, energy, angular momentum, and nuclear spin. Full scrambling of all five nuclei during the collision is assumed for the calculations and alternatively partial dynamical restrictions are considered. The ergodic principle of the collision is employed in two limiting cases, neglecting (weak ergodic limit) or accounting for explicit degeneracies of the reaction mechanisms (strong ergodic limit). The resulting sets of rate coefficients are shown to be consistent with the detailed balance and thermodynamical equilibrium constants. Rate coefficients, k ( T ) , for the deuteration chain of H 3 + with HD as well as H 2 D + ∕ H 3 + equilibrium ratios have been measured in a variable temperature 22-pole ion trap. In particular, the D 2 H + + HD → D 3 + + H 2 rate coefficient indicates a change in reaction mechanism when going to higher temperatures. The good overall agreement between experiment and theory encourages the use of the theoretical predictions for astrophysical modeling.