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Catalytic behaviour of dense hot water

Nature Chemistry volume 1, pages 57–62 (2009)Cite this article

Abstract

Water is known to exhibit fascinating physical properties at high pressure and temperature. Its remarkable structural and phase complexities suggest the possibility of exotic chemical reactivity under extreme conditions, although this remains largely unstudied. Detonations of high explosives containing oxygen and hydrogen produce water at thousands of kelvin and tens of gigapascals, similar to conditions in the interiors of giant planets. These systems thus provide a unique means of elucidating the chemistry of ‘extreme water’. Here, we show that water has an unexpected role in catalysing complex explosive reactions—contrary to the current view that it is simply a stable detonation product. Using first-principles atomistic simulations of the detonation of the high explosive pentaerythritol tetranitrate, we discovered that H2O (source), H (reducer) and OH (oxidizer) act as a dynamic team that transports oxygen between reaction centres. Our finding suggests that water may catalyse reactions in other explosives and in planetary interiors.

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Figure 1: Initial MD configuration and example simulation snapshots.
Figure 2: Catalytic cycle of local reaction centres, demonstrating oxygen transportation from nitrogen to carbon and hydrogen.
Figure 3: Overwhelming participation of hydrogen in the majority of reactions.
Figure 4: Hydrogen is more mobile than other heavier atoms.
Figure 5: Atomic charge distributions obtained at the Chapman–Jouguet condition.

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Acknowledgements

This work was performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory (LLNL) under Contract DE-AC52-07NA27344. The project 06-SI-005 was funded by the Laboratory Directed Research and Development Program at LLNL. The authors would like to express their sincere appreciation to E. Reed for useful discussion and to L. Krauss, K. Kline and J. McInnis for their contributions to the preparation of the manuscript and figures.

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Authors and Affiliations

  1. Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, 94551, California, USA

    Christine J. Wu, Laurence E. Fried, Lin H. Yang, Nir Goldman & Sorin Bastea

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  1. Christine J. Wu
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  2. Laurence E. Fried
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  3. Lin H. Yang
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Contributions

C.J.W. originated the central idea, performed and analysed the PETN MD simulations, and wrote the paper; L.E.F. developed the molecular analyser code and contributed to the writing of the paper; L.H.Y. carried out Quantum MD code development; N.G. contributed to Mulliken charge analysis; S.B. performed conductivity and dielectric constant calculations; all of the authors contributed to discussions and editing of the manuscript.

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Correspondence to Christine J. Wu.

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Wu, C., Fried, L., Yang, L. et al. Catalytic behaviour of dense hot water. Nature Chem 1, 57–62 (2009). https://doi.org/10.1038/nchem.130

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