Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane.

We present a combined experimental and theoretical investigation of the autoignition chemistry of a prototypical cyclic hydrocarbon, cyclopentane. Experiments using a high-pressure photolysis reactor coupled to time-resolved synchrotron VUV photoionization mass spectrometry directly probe the short-lived radical intermediates and products in cyclopentane oxidation reactions. We detect key peroxy radical intermediates ROO and OOQOOH, as well as several hydroperoxides, formed by second O addition.

Finding reaction mechanisms, intuitive or otherwise.

Chemical reaction mechanisms have been frequently studied using computational simulations, but these tools have been primarily effective at examining reaction paths within the scope of chemical intuition. To determine reaction mechanisms that were not already preconceived by chemists, nonstandard simulation tools are required. This perspective introduces new methods developed by the Zimmerman group that are designed to uncover sequences of elementary steps, from first principles and without substantial human guidance.