The dynamics of the hydrogen exchange reaction at 2.20 eV collision energy: Comparison of experimental and theoretical differential cross sections

摘要

The H + D_2 (v = 0, j = 0) -> HD(v', j') + D isotopic variant of the hydrogen atom exchange reaction has been studied in a crossed molecular beam experiment at a collision energy of 2.20 eV. Kinetic energy spectra of the nascent D atoms were obtained by using the Rydberg atom time-of-flight technique. The extensive set of spectra collected has permitted the derivation of rovibrationally state-resolved differential cross sections in the center-of-mass frame for most of the internal states of the HD product molecules, allowing a direct comparison with theoretical predictions. Accurate 3D quantum mechanical calculations have been carried out on the refined version of the latest Boothroyd-Keogh-Martin-Peterson potential energy surface, yielding and excellent agreement with the experimentally determined differential cross sections. The comparison of the results from quasi-classical trajectory calculations on the same potential surface reveals some discrepancies with the measured data, but shows a good global accordance. The theoretical calculations demonstrate that, at this energy, reactive encounters are predominantly noncollinear and that collinear collisions lead mostly to nonreactive recrossing. The experimental results are satisfactorily accounted for by theoretical calculations without consideration of Geometric Phase effects.