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An experimental and theoretical investigation of the collision energy dependence of the HD(ν[sup ′]=2,j[sup ′]) rotational product state distribution for the H+D[sub 2] reaction in the collision energy range of E[sub col]=1.30–1.89 eV has been carried out. Theoretical results based on time-dependent and time-independent quantum mechanical methods agree nearly perfectly with each other, and the agreement with the experiment is good at low collision energies and very good at high collision energies. This behavior is in marked contrast to a previous report on the HD(ν[sup ′]=3,j[sup ′]) product state rotational distribution [Pomerantz et al., J. Chem. Phys. 120, 3244 (2004)] where a systematic difference between experiment and theory was observed, especially at the highest collision energies. The reason for this different behavior is not yet understood. In addition, this study employs Doppler-free spectroscopy to resolve an ambiguity in the E, F–X resonantly enhanced multiphoton ionization transition originating from the HD(ν[sup ′]=2,j[sup ′]=1) state, which is found to be caused by an accidental blending with the transition coming from the HD(ν[sup ′]=1,j[sup ′]=14) state. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present experimental rotational distributions for the reaction H+D[sub 2]→HD(ν[sup ′]=3,j[sup ′])+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[sup ′] plot). To compare with the experimental data, we also present E–j[sup ′] 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. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]