Disagreement between theory and experiment in the simplest chemical reaction: collision energy dependent rotational distributions for H + D2 --> HD(nu' = 3,j') + D.

Abstract

We present experimental rotational distributions for the reaction H + D2 --> HD(nu' = 3,j') + D at eight different collision energies between 1.49 and 1.85 eV. We combine a previous measurement of the state-resolved excitation function for this reaction [Ayers et al., J. Chem. Phys. 119, 4662 (2003)] with the current data to produce a map of the relative reactive cross section as a function of both collision energy and rotational quantum number (an E-j' plot). To compare with the experimental data, we also present E-j' plots resulting from both time-dependent and time-independent quantum mechanical calculations carried out on the BKMP2 surface. The two calculations agree well with each other, but they produce rotational distributions significantly colder than the experiment, with the difference being more pronounced at higher collision energies. Disagreement between theory and experiment might be regarded as surprising considering the simplicity of this system; potential causes of this discrepancy are discussed.