The past two decades have seen rapid developments in short-pulse X-ray sources, which have enabled the study of nuclear and electronic dynamics by ultrafast X-ray spectroscopies with unprecedented time resolution ranging from nanoseconds to attoseconds. In this Perspective, we discuss some of the major achievements in the study of nuclear and electronic dynamics with X-ray pulses produced by high-harmonic, free-electron-laser and synchrotron sources. The particular dynamic processes probed by X-ray radiation highlighted in this Perspective are electronic coherences on attosecond to femtosecond timescales, chemical reactions, such as dissociations, and pericyclic ring-openings, spin-crossover dynamics, ligand-exchange dynamics and structural deformations in excited states. X-ray spectroscopic probing of chemical dynamics holds great promise for the future owing to the ongoing developments of new spectroscopies, such as four-wave mixing, and the continuous improvements in emerging laboratory-based, high-harmonic sources and large-scale, facility-based, free-electron lasers.
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We acknowledge funding from the Air Force Office of Scientific Research (AFOSR) (grant nos. FA9550-15-1-0037 and FA9550-14-1-0154), the Army Research Office (ARO) (WN911NF- 14-1-0383), the Office of Assistant Secretary of Defense for Research and Engineering through a National Security Science and Engineering Faculty Fellowship (NSSEFF), the W. M. Keck Foundation, the Defense Advanced Research Projects Agency PULSE program through grant W31P4Q-13-1-0017 and the National Science Foundation (NSF) through grants CHE-1361226 and CHE-1660417, and through a Foundation Major Research Instrumentation (NSF MRI) grant #1624322. Further funding was provided by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Atomic, Molecular and Optical Sciences Program, Physical Chemistry of Inorganic Nanostructures Program and Gas Phase Chemical Physics Program under contract no. DE-AC02-05-CH11231. P.M.K. acknowledges support from the Swiss National Science Foundation (grant nos. P2EZP2 165252 and P300P2 174293). M.Z. acknowledges support from the Humboldt Foundation. S.K.C. is supported by the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE) Postdoctoral Research Award under the EERE Solar Energy Technologies Office.
Nature Reviews Chemistry thanks G. Cerullo and L. X. Chen for their contribution to the peer review of this work.
The authors declare that they have no competing financial interests.
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Kraus, P.M., Zürch, M., Cushing, S.K. et al. The ultrafast X-ray spectroscopic revolution in chemical dynamics. Nat Rev Chem 2, 82–94 (2018). https://doi.org/10.1038/s41570-018-0008-8
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