Abstract
Since the end of the 1960th, the Woodward–Hoffmann rules have been a well-grounded and powerful tool to understand and predict pericyclic reactions. Recently, astonishing results on such reactions subject to mechanochemical activation by external forces have revealed reaction pathways at sufficiently large forces which are not expected from the Woodward–Hoffmann rules. These findings have started a controversy whether the “Woodward–Hoffmann rules are broken in mechanochemistry”. Our study of ring opening of cyclopropane shows that the electronic structure underlying the dis- and conrotatory pathways, which are greatly distorted upon applying forces to an extent that eventually the “thermally forbidden” process becomes “mechanochemically allowed”, does not change. It is rather the mechanical work that lowers the activation barrier and therefore promotes reaction pathways to products not expected from the Woodward–Hoffmann rules. A front cover and an additional cover profile article have been devoted to these findings (Wollenhaupt et al., Chem Phys Chem 16:1593–1597, 2015)
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Acknowledgements
Partial financial support is provided by the DFG Koselleck Grant “Understanding Mechanochemistry” to Dominik Marx We wish to thank Przemyslaw Dopieralski and Martin Krupička for their contributions to this work. Computer resources have kindly been provided by HLRS Stuttgart (account ID 12982). Calculations were run using the distributed memory (MPI) parallelization scheme. In most runs 192 cores (6 nodes in the Hornet system) were used, with an average wall time of about 5.8 h (equivalent to ca. 1100 core-hours per run). A few runs were performed using 128 cores (4 nodes in Hornet) with an average wall time of about 9.1 h (ca. 1100 core-hours per run), whereas another group of runs were done using 256 cores (8 nodes in Hornet) with an average wall time of about 5.3 h (ca. 1300 core-hours). The requirement of RAM for each of these runs was on average 15 GB of total memory (2.5 GB per node for most runs). A typical run required approximately 1.5 GB of disk space for permanent data storage and an additional 4.5 GB for scratch data.
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Wollenhaupt, M., Zoloff, M., Marx, D. (2016). Mechanochemistry of Cyclopropane Ring-Opening Reactions. In: Nagel, W., Kröner, D., Resch, M. (eds) High Performance Computing in Science and Engineering ’15. Springer, Cham. https://doi.org/10.1007/978-3-319-24633-8_15
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DOI: https://doi.org/10.1007/978-3-319-24633-8_15
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