First accurate experimental study of Mu reactivity from a state-selected reactant in the gas phase: the Mu + H2{1} reaction rate at 300 K

This paper reports on the experimental background and methodology leading to recent results on the first accurate measurement of the reaction rate of the muonium (Mu) atom from a state-selected reactant in the gas phase: the Mu + H2{1}→ MuH + H reaction at 300 K, and its comparison with rigorous quantum rate theory, Bakule et al (2012 J. Phys. Chem. Lett. 3 2755). Stimulated Raman pumping, induced by 532 nm light from the 2nd harmonic of a Nd:YAG laser, was used to produce H2 in its first vibrational (v = 1) state, H2{1}, in a single Raman/reaction cell. A pulsed muon beam (from 'ISIS', at 50 Hz) matched the 25 Hz repetition rate of the laser, allowing data taking in equal 'Laser-On/Laser-Off' modes of operation. The signal to noise was improved by over an order of magnitude in comparison with an earlier proof-of-principle experiment. The success of the present experiment also relied on optimizing the overlap of the laser profile with the extended stopping distribution of the muon beam at 50 bar H2 pressure, in which Monte Carlo simulations played a central role. The rate constant, found from the analysis of three separate measurements, which includes a correction for the loss of H2{1} concentration due to collisional relaxation with unpumped H2 during the time of each measurement, is kMu{1} = 9.9[(−1.4)(+1.7)] × 10−13 cm3 s−1 at 300 K. This is in good to excellent agreement with rigorous quantum rate calculations on the complete configuration interaction/Born–Huang surface, as reported earlier by Bakule et al, and which are also briefly commented on herein. (paper)