The H-2(+) + Hd Reaction At Low Collision Energies: H-3(+)/H2d+ Branching Ratio And Product-Kinetic-Energy Distributions

The fully state-selected reactions between H-2(+) molecules in the X+ 2 sigma(+)(g)(v(+) = 0, N+ = 0) state and HD molecules in the X (1)sigma(+)(g)(v = 0, J = 0) state forming H-3(+) + D and H2D+ + H have been studied at collision energies E-coll between 0 and k(B)center dot 30 K with a resolution of about 75 mK at the lowest energies. H-2 molecules in a supersonic beam were prepared in Rydberg-Stark states with principal quantum number n = 27 and merged with a supersonic beam of ground-state HD molecules using a curved surface-electrode Rydberg-Stark decelerator and deflector. The reaction between H-2(+) and HD was studied within the orbit of the Rydberg electron to avoid heating of the ions by stray electric fields. The reaction was observed for well-defined and adjustable time intervals, called reaction-observation windows, between two electric-field pulses. The first pulse swept all ions away from the reaction volume and its falling edge defined the beginning of the reaction-observation window. The second pulse extracted the product ions toward a charged-particle detector located at the end of a time-of-flight tube and its rising edge defined the end of the reaction-observation window. Monitoring and analysing the time-of-flight distributions of the H-3(+) and H2D+ products in dependence of the duration of the reaction-observation window enabled us to obtain information on the kinetic-energy distribution of the product ions and determine branching ratios of the H-3(+) + D and H2D+ + H reaction channels. The mean product-kinetic-energy release is 0.46(5) eV, representing 27(3)% of the available energy, and the H-3(+) + D product branching ratio is 0.225(20). The relative reaction rates correspond closely to Langevin capture rates down to the lowest energies probed experimentally (approximate to k(B)center dot 50 mK).