title: Stereodynamics of the F + HD(v = 0, j = 1) reaction: direct vs. resonant mechanisms.
abstract: The stereodynamics and mechanism of the F + HD(v = 0, j = 1) → HF (DF) + D (H) reactions have been thoroughly analysed at collision energies in the 0-160 meV range. Specifically, this study is focused on (i) the comparison between the stereodynamics of the collisions leading to HF and DF formation, and (ii) the stereodynamical fingerprints of the resonance that occurs at low collision energies in the HF channel and whose manifestation in the total cross section is greatly diminished for initial j > 0. While previous studies were limited to the analysis of integral cross sections (ICS), differential cross sections (DCS) and reaction probabilities, in the present work we have included the analysis of vectorial quantities such as the direction of the initial rotational angular momentum and internuclear axis, and their effect on reactivity. In particular, polarisation parameters (PP) and polarisation dependent differential cross sections (PDDCS), quantities that describe how the intrinsic HD rotational angular momentum and molecular axis polarisations contribute to reaction, are calculated and examined. The evolution of the PPs with the collision energy differs markedly between the two reaction channels. For the DF channel, the PP values are small and change very little in the energy range in which DF formation is appreciable. In contrast, rapid fluctuations in the magnitude and sign of the PPs are observed in the HF channel at low collision energies in and around the resonance. As the collision energy increases, direct (non-resonant) scattering prevails, and the various quantities are reasonably well accounted for by the QCT calculations, as in the case of the DF channel. The intrinsic directional information has been used to access the extent of control that can be achieved through polarisation of the HD molecule prior to collision. It was found that the same extrinsic preparation leads to very different outcomes on the HF channel DCS when the collision energy is close to the resonance. It is also shown that polarisation of the HD internuclear axis along the initial relative velocity enhances the effect of the resonance and allows its clear identification. Finally, the effect of different extrinsic preparations on the angle-velocity DCS is found to be strong, thus allowing considerable control of product angular distributions.
authors.affiliation: Grupo de Dinámica Molecular, Departamento de Química Física, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008 Salamanca, Spain. jalde@usal.es
authors.forename: Jesús
authors.initials: J
authors.lastname: Aldegunde
authors.forename: Pablo G
authors.initials: PG
authors.lastname: Jambrina
authors.forename: Marcelo P
authors.initials: MP
authors.lastname: de Miranda
authors.forename: Vicente
authors.initials: V
authors.lastname: Sáez Rábanos
authors.forename: F Javier
authors.initials: FJ
authors.lastname: Aoiz