Abstract
Chemical Kinetics Carbon-centered radicals containing the hydroperoxy group, commonly denoted as •QOOH, are elusive but are among the most critical intermediate species for kinetic modeling of hydrocarbon oxidation in various atmospheric and combustion processes. Their direct experimental observation is a long-standing challenge, with only one successful previous attempt. Using a combination of infrared activation spectroscopy and ultraviolet laser–induced fluorescence detection, Hansen et al. directly characterized the vibrational structure of a •QOOH intermediate in isobutane oxidation, collisionally stabilized and isolated, and followed its dissociative evolution under infrared activation with time and energy resolution. High-level electronic structure calculations revealed an important role of heavy-atom tunneling in this process. Science , abj0412, this issue p. [679][1] [1]: /lookup/doi/10.1126/science.abj0412
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