Enhanced reactivity of fluorine with para-hydrogen in cold interstellar clouds by resonance-induced quantum tunnelling.

ABSTRACT

Chemical reactions are important in the evolution of low-temperature interstellar clouds, where the quantum tunnelling effect becomes significant. The F + para-H2 → HF + H reaction, which has a significant barrier of 1.8 kcal mol-1, is an important source of HF in interstellar clouds; however, the dynamics of this quantum-tunnelling-induced reactivity at low temperature is unknown. Here, we show that this quantum tunnelling is caused by a post-barrier resonance state. Quantum-state-resolved crossed-beam scattering measurements reveal that this resonance state has a collision energy of ~5 meV and a lifetime of ~80 fs, which are in excellent agreement with a recent anion photoelectron spectroscopic study. Accurate quantum reactive scattering calculations on the new iCSZ-LWAL potential energy surfaces provides a detailed explanation of the experimental results. The reaction rate for this system was also theoretically determined accurately at temperatures as low as 1 K.