Hydrogen atom quantum diffusion in solid parahydrogen: The H + N₂O → cis-HNNO → trans-HNNO reaction

The diffusion and reactivity of hydrogen atoms in solid parahydrogen at temperatures between 1.5 K and 4.3 K are investigated by high-resolution infrared spectroscopy. Hydrogen atoms are produced within solid parahydrogen as the by-products of the 193 nm in situ photolysis of N₂O, which induces a two-step tunneling reaction, H + N₂O → cis-HNNO → trans-HNNO. The second-order rate constant for the first step to form cis-HNNO is found to be inversely proportional to the N₂O concentration after photolysis, indicating that the hydrogen atoms move through solid parahydrogen via quantum diffusion. This reaction only readily occurs at temperatures below 2.8 K, not due to an increased rate constant for the first reaction step at low temperatures but rather due to an increased selectivity to the reaction. The rate constant for the second step of the reaction mechanism involving unimolecular isomerization is shown to be independent of the N₂O concentration as expected. The inverse concentration dependence of the rate constant for the reaction step that involves the hydrogen atom demonstrates clearly that quantum diffusion influences the reactivity of the hydrogen atoms in solid parahydrogen, which does not have an analogy in classical reaction kinetics.