Concluding remarks: Faraday Discussion on unimolecular reactions.

This Faraday Discussion , marking the centenary of Lindemann's explanation of the pressure-dependence of unimolecular reactions, presented recent advances in measuring and computing collisional energy transfer efficiencies, microcanonical rate coefficients, and pressure-dependent (phenomenological) rate coefficients, and the incorporation of these rate coefficients in kinetic models. Several of the presentations featured systems where breakdown of the Born-Oppenheimer approximation is key to understanding the measured rates/products. Many of the reaction systems presented were quite complex, which can make it difficult to go from "plausible proposed explanation" to "quantitative agreement between model and experiment". This complexity highlights the need for better automation of the calculations, better documentation and benchmarking to catch any errors and to make the calculations more easily reproducible, and continued (and even closer) cooperation of experimentalists and modelers. In some situations the correct definition of a "species" is debatable, since the population distributions and time evolution are so distorted from the perfect-Boltzmann Lewis-structure zero-order concept of a chemical species. Despite all these challenges, the field has made tremendous advances, and several cases were presented which demonstrated both excellent understanding of very complicated reaction chemistry and quantitatively accurate predictions of complicated experiments. Some of the interesting contributions to this Discussion are highlighted here, with some comments and suggestions for next steps.