Stereodynamical control of the H + HD → H + D reaction through HD reagent alignment.

Prealigning nonpolar reacting molecules leads to large stereodynamical effects because of their weak steering interaction en route to the reaction barrier. However, experimental limitations in preparing aligned molecules efficiently have hindered the investigation of steric effects in bimolecular reactions involving hydrogen. Here, we report a high-resolution crossed-beam study of the reaction H + HD( = 1, = 2) → H(', ') + D at collision energies of 0.50, 1.20, and 2.07 electron volts in which the vibrationally excited hydrogen deuteride (HD) molecules were prepared in two collision configurations, with their bond preferentially aligned parallel and perpendicular to the relative velocity of collision partners. Notable stereodynamical effects in differential cross sections were observed. Quantum dynamics calculations revealed that strong constructive interference in the perpendicular configuration plays an important role in the stereodynamical effects observed.