Enhancing reactivity of SiO⁺ ions by controlled excitation to extreme rotational states

Optical pumping of molecules provides unique opportunities for control of chemical reactions at a wide range of rotational energies. This work reports a chemical reaction with extreme rotational excitation of a reactant and its kinetic characterization. We investigate the chemical reactivity for the hydrogen abstraction reaction SiO⁺ + H₂ → SiOH⁺ + H in an ion trap. The SiO⁺ cations are prepared in a narrow rotational state distribution, including super-rotor states with rotational quantum number (j) as high as 170, using a broad-band optical pumping method. We show that the super-rotor states of SiO⁺ substantially enhance the reaction rate, a trend reproduced by complementary theoretical studies. We reveal the mechanism for the rotational enhancement of the reactivity to be a strong coupling of the SiO⁺ rotational mode with the reaction coordinate at the transition state on the dominant dynamical pathway.