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Resonant Auger decay driving intermolecular Coulombic decay in molecular dimers

Abstract

In 1997, it was predicted1 that an electronically excited atom or molecule placed in a loosely bound chemical system (such as a hydrogen-bonded or van-der-Waals-bonded cluster) could efficiently decay by transferring its excess energy to a neighbouring species that would then emit a low-energy electron. This intermolecular Coulombic decay (ICD) process has since been shown to be a common phenomenon2,3,4,5,6,7,8,9,10,11,12, raising questions about its role in DNA damage induced by ionizing radiation, in which low-energy electrons are known to play an important part13,14. It was recently suggested15 that ICD can be triggered efficiently and site-selectively by resonantly core-exciting a target atom, which then transforms through Auger decay into an ionic species with sufficiently high excitation energy to permit ICD to occur. Here we show experimentally that resonant Auger decay can indeed trigger ICD in dimers of both molecular nitrogen and carbon monoxide. By using ion and electron momentum spectroscopy to measure simultaneously the charged species created in the resonant-Auger-driven ICD cascade, we find that ICD occurs in less time than the 20 femtoseconds it would take for individual molecules to undergo dissociation. Our experimental confirmation of this process and its efficiency may trigger renewed efforts to develop resonant X-ray excitation schemes16,17 for more localized and targeted cancer radiation therapy.

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Figure 1: The overall decay cascade mechanism.
Figure 2: Experimental results.

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Acknowledgements

This work was supported by the Deutsche Forschungsgemeinschaft and the Deutscher Akademischer Austauschdienst. We thank the staff of the Advanced Light Source for excellent support during the beam time. This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, and by the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy at the Lawrence Berkeley National Laboratory under contract number DE-AC02-05CH11231. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract number DE-AC02-05CH11231. We thank K. Gokhberg and L. Cederbaum for suggesting this experiment and for many discussions. M.S.S. thanks the Alexander von Humboldt foundation for financial support.

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All authors contributed to the experiment. F.T. and T.J. performed the data analysis. All authors contributed to the manuscript.

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Correspondence to F. Trinter or T. Jahnke.

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The authors declare no competing financial interests.

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Trinter, F., Schöffler, M., Kim, HK. et al. Resonant Auger decay driving intermolecular Coulombic decay in molecular dimers. Nature 505, 664–666 (2014). https://doi.org/10.1038/nature12927

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