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.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Cederbaum, L. S., Zobeley, J. & Tarantelli, F. Giant intermolecular decay and fragmentation of clusters. Phys. Rev. Lett. 79, 4778–4781 (1997)
Jahnke, T. et al. Ultrafast energy transfer between water molecules. Nature Phys. 6, 139–142 (2010)
Mucke, M. et al. A hitherto unrecognized source of low-energy electrons in water. Nature Phys. 6, 143–146 (2010)
Kim, H.-K. et al. Enhanced production of low energy electrons by alpha particle impact. Proc. Natl Acad. Sci. USA 108, 11821–11824 (2011)
Barth, S. et al. Observation of resonant interatomic Coulombic decay in Ne clusters. J. Chem. Phys. 122, 241102 (2005)
Aoto, T. et al. Properties of resonant interatomic Coulombic decay in Ne dimers. Phys. Rev. Lett. 97, 243401 (2006)
Jahnke, T. et al. Experimental separation of virtual photon exchange and electron transfer in interatomic Coulombic decay of neon dimers. Phys. Rev. Lett. 99, 153401 (2007)
Ueda, K. et al. Interatomic Coulombic decay following the Auger decay: experimental evidence in rare-gas dimers. J. Electron Spectrosc. Relat. Phenom. 166–167, 3–10 (2008)
Grieves, G. A. & Orlando, T. M. Intermolecular Coulomb decay at weakly coupled heterogeneous interfaces. Phys. Rev. Lett. 107, 016104 (2011)
Marburger, S., Kugeler, O., Hergenhahn, U. & Möller, T. Experimental evidence for interatomic Coulombic decay in Ne clusters. Phys. Rev. Lett. 90, 203401 (2003)
Jahnke, T. et al. Experimental observation of interatomic Coulombic decay in neon dimers. Phys. Rev. Lett. 93, 163401 (2004)
Öhrwall, G. et al. Femtosecond interatomic Coulombic decay in free neon clusters: large lifetime differences between surface and bulk. Phys. Rev. Lett. 93, 173401 (2004)
Boudaïffa, B., Cloutier, P., Hunting, D., Huels, M. A. & Sanche, L. Resonant formation of DNA strand breaks by low-energy (3 to 20 eV) electrons. Science 287, 1658–1660 (2000)
Hanel, G. et al. Electron attachment to uracil: effective destruction at subexcitation energies. Phys. Rev. Lett. 90, 188104 (2003)
Gokhberg, K., Kolorenč, P., Kuleff, A. I. & Cederbaum, L. S. Site- and energy-selective slow-electron production through intermolecular Coulombic decay. Nature http://dx.doi.org/10.1038/nature12936 (this issue)
Pradhan, A. K. et al. Resonant X-ray enhancement of the Auger effect in high-Z atoms, molecules, and nanoparticles: potential biomedical applications. J. Phys. Chem. A 113, 12356–12363 (2009)
Howell, R. W. Auger processes in the 21st century. Int. J. Radiat. Biol. 84, 959–975 (2008)
Botting, S. K. & Lucchese, R. R. Auger decay of the C 1s -> 2π* excitation of CO. Phys. Rev. A 56, 3666–3674 (1997)
Aquilanti, V., Bartolomei, M., Cappelletti, D., Carmona-Novillo, E. & Pirani, F. The N2–N2 system: an experimental potential energy surface and calculated rotovibrational levels of the molecular nitrogen dimer. J. Chem. Phys. 117, 615 (2002)
Havenith, M., Petri, M., Lubina, C., Hilpert, G. & Urban, W. J. IR spectroscopy of (CO)2 using concentration-frequency double modulation in a supersonic jet expansion. J. Mol. Spectrosc. 167, 248–261 (1994)
Meredith, A. W. & Stone, A. J. An ab initio and diffusion Monte Carlo study of the potential energy surface of the CO dimers. J. Phys. Chem. A 102, 434–445 (1998)
Havermeier, T. et al. Single photon double ionization of the helium dimer. Phys. Rev. Lett. 104, 153401 (2010)
Baltzer, P. et al. Inner-valence states of CO+ between 22 eV and 46 eV studied by high resolution photoelectron spectroscopy and ab initio CI calculations. J. Phys. At. Mol. Opt. Phys. 27, 4915 (1994)
Kimura, M. et al. Efficient site-specific low-energy electron production via interatomic Coulombic decay following resonant Auger decay in argon dimers. Phys. Rev. A 87, 043414 (2013)
O’Keeffe, P. et al. The role of the partner atom and resonant excitation energy in interatomic Coulombic decay in rare gas dimers. J. Phys. Chem. Lett. 4, 1797–1801 (2013)
Kimura, K. et al. Controlling low-energy electron emission via resonant-auger-induced interatomic Coulombic decay. J. Phys. Chem. Lett. 4, 1838–1842 (2013)
Dörner, R. et al. Cold target ion momentum spectrocopy: a ‘momentum microscope’ to view atomic collisions dynamics. Phys. Rep. 330, 95–192 (2000)
Ullrich, J. et al. Recoil-ion and electron momentum spectroscopy: reaction-microscopes. Rep. Prog. Phys. 66, 1463 (2003)
Schöffler, M. S. et al. Matter wave optics perspective at molecular photoionization: K-shell photoionization and Auger decay of N2 . New J. Phys. 13, 095013 (2011)
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.
Author information
Authors and Affiliations
Contributions
All authors contributed to the experiment. F.T. and T.J. performed the data analysis. All authors contributed to the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing financial interests.
PowerPoint slides
Rights and permissions
About this article
Cite this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nature12927
This article is cited by
-
Tunnelling of electrons via the neighboring atom
Light: Science & Applications (2024)
-
Radiation damage by extensive local water ionization from two-step electron-transfer-mediated decay of solvated ions
Nature Chemistry (2023)
-
Experimental quantification of site-specific efficiency of Interatomic Coulombic Decay after inner shell ionization
Communications Physics (2023)
-
The origin of enhanced \({{{{{{{{\rm{O}}}}}}}}}_{2}^{+}\) production from photoionized CO2 clusters
Communications Chemistry (2022)
-
Triple ionization and fragmentation of benzene trimers following ultrafast intermolecular Coulombic decay
Nature Communications (2022)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
