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Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry

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Abstract

Termolecular association reactions involve ephemeral collision complexes—formed from the collision of two molecules—that collide with a third and chemically inert ‘bath gas’ molecule that simply transfers energy to/from the complex. These collision complexes are generally not thought to react chemically on collision with a third molecule in the gas-phase systems of combustion and planetary atmospheres. Such ‘chemically termolecular’ reactions, in which all three molecules are involved in bond making and/or breaking, were hypothesized long ago in studies establishing radical chain branching mechanisms, but were later concluded to be unimportant. Here, with data from ab initio master equation and kinetic-transport simulations, we reveal that reactions of H + O2 collision complexes with other radicals constitute major kinetic pathways under common combustion situations. These reactions are also found to influence flame propagation speeds, a common measure of global reactivity. Analogous chemically termolecular reactions mediated by ephemeral collision complexes are probably of significance in various combustion and planetary environments.

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Figure 1: Results from simulations of flames propagating into a hydrogen–air mixture with a hydrogen mole fraction X H 2 of 0.5 at atmospheric pressure and temperature.
Figure 2: Fraction of total HO2 + R reaction flux through H + O2 + R, fH+O2+R = ωH+O2+R/(ωH+O2+R + ωHO2+R) and peak radical mole fractions XR, in flames propagating through hydrogen–air mixtures.
Figure 3: Contribution of chemically termolecular reactions mediated by ephemeral HO2** collision complexes to the planar flame propagation speed suo.

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Acknowledgements

This material is based on work supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under contract no. DE-AC02-06CH11357. M.P.B. acknowledges financial support from Columbia University.

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Authors and Affiliations

  1. Department of Mechanical Engineering, Department of Chemical Engineering, Data Science Institute, Columbia University, New York, 10027, New York, USA

    Michael P. Burke

  2. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Stephen J. Klippenstein

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  1. Michael P. Burke
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  2. Stephen J. Klippenstein
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Contributions

M.P.B. and S.J.K. conceived and designed the calculations. M.P.B. performed the master equation calculations with technical input from S.J.K., and M.P.B. performed the kinetic-transport calculations. Both authors contributed to writing the paper.

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Correspondence to Michael P. Burke.

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Burke, M., Klippenstein, S. Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry. Nature Chem 9, 1078–1082 (2017). https://doi.org/10.1038/nchem.2842

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