Selected ion flow drift tube studies of the reactions of Si+(2P) with HCl, H2O, H2S, and NH3: Reactions which produce atomic hydrogen

Abstract

The reaction rate coefficients, k, for the reactions of ground-state Si+(2P) with HCl, H2O, H2S, and NH3, have been measured as a function of reactant ion/reactant neutral center-of-mass kinetic energy, KECM, in a selected ion flow drift tube (SIFDT) apparatus, operated with helium at a temperature 298±2 K. The values k of the studied reactions have very pronounced, negative energy dependencies; the rate coefficients decrease by about 1 order of magnitude as KECM increase from near thermal values to ∼2 eV. The results are interpreted in terms of a simple model assuming the reactions to proceed via the formation of long-lived complexes. These intermediate complexes decompose back to reactants or forward to products, the unimolecular decomposition rate coefficients for these reactions being k1 and k2, respectively. It is found that a power law of the form k−1/k2=const(KECM)m closely describes each reaction.