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Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction
Abstract
X-ray vision catches Woodward-Hoffmann: The celebrated Woodward-Hoffmann (W-H) rules rationalize a variety of rapid bond rearrangements in organic molecules. The key insight involved symmetry conservation in the electronic journey from reactant to product. Attar et al. now report femtosecond x-ray absorption spectra and accompanying simulation studies that track shifts in carbon electronic states during one such reaction: the photochemical ring opening of cyclohexadiene to hexatriene (see the Perspective by Sension). The smooth evolution that occurs in the vicinity of the pericyclic minimum provides direct affirmation of the W-H framework. Moreover, the use of a convenient tabletop apparatus bodes well for future x-ray studies of ultrafast electronic dynamics. Science , this issue p. 54 ; see also p. 31
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“At photon energies up to 300 eV, the state-ofthe-art in x-ray transient-absorption dynamics (based on femtosecond high harmonics) has been used to measure excited-state ring opening of cyclohexadiene [216] (figure 26)”
From Roadmap of ultrafast x-ray atomic and molecular physics (2018) · cites this paper as [216]
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“X-ray fs identification of the key transition state labeled 2 A, blue points, for ring opening of cyclohexadiene.”
From Roadmap of ultrafast x-ray atomic and molecular physics (2018) · cites this paper as [216]
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Panman, M. R., Biasin, E., Berntsson, O., Hermann, M., Niebling, S., Hughes, A. J., Kübel, J., Atkovska, K., Gustavsson, E., Nimmrich, A., et al. (2020) · Physical Review Letters · doi:10.1103/physrevlett.125.226001 · Cited by 37
Segatta, F., Nenov, A., Orlandi, S., Arcioni, A., Mukamel, S., & Garavelli, M. (2019) · Faraday Discussions · doi:10.1039/c9fd00073a · Cited by 36
Single-Molecule Observation of the Intermediates in a Catalytic Cycle
Ramsay, W. J., Bell, N. A. W., Qing, Y., & Bayley, H. (2018) · Journal of the American Chemical Society · doi:10.1021/jacs.8b09282 · Cited by 35
Kleine, C., Winghart, M., Zhang, Z.-Y., Richter, M., Ekimova, M., Eckert, S., Vrakking, M. J. J., Nibbering, E. T. J., Rouzée, A., & Grant, E. R. (2022) · Physical Review Letters · doi:10.1103/physrevlett.129.123002 · Cited by 35
Kubin, M., Guo, M., Ekimova, M., Baker, M. L., Kröll, T., Källman, E., Kern, J. F., Yachandra, V. K., Yano, J., Nibbering, E. T. J., et al. (2018) · Inorganic Chemistry · doi:10.1021/acs.inorgchem.8b00419 · Cited by 34
“Based on an extrapolation of our results we now discuss the application of L-edge XAS with a transmission flatjet to other experimental designs with, first, low sample concentrations on the order of 1 mM as achieved for many biologically relevant samples 12 and, second, with lower photon fluxes, as available for examp…”
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Ehlert, C., Gühr, M., & Saalfrank, P. (2018) · The Journal of Chemical Physics · doi:10.1063/1.5050488 · Cited by 32
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Chang, K. F., Wang, H., Poullain, S. M., Prendergast, D., Neumark, D. M., & Leone, S. R. (2021) · The Journal of Chemical Physics · doi:10.1063/5.0056299 · Cited by 32
Self-citationTudorovskaya, M., Minns, R. S., & Kirrander, A. (2018) · Physical Chemistry Chemical Physics · doi:10.1039/c8cp02397b · Cited by 32
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“Thus far, despite encouraging progress 38,40,53 , identifying the ultrafast pathways with their expected electronic and vibrational coherences has been obscured by the challenge of temporally resolving and spectrally identifying them directly 19,54 .”
Pump-Probe Ghost Imaging with SASE FELs
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Attosecond soft X-ray high harmonic generation
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Extension of water-window harmonic cutoff by laser defocusing-assisted phase matching
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Spin-optotronic Properties of Organometal Halide Perovskites
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Hekele, J., Yao, Y., Kanai, Y., Blüm, V., & Kratzer, P. (2021) · The Journal of Chemical Physics · doi:10.1063/5.0066753 · Cited by 30
Metadata
- Authors
- Attar, A. R., Bhattacherjee, A., Pemmaraju, C. D., Schnorr, K., Closser, K. D., Prendergast, D., & Leone, S. R.
- Affiliations
- Lawrence Berkeley National Laboratory (US)
- Corresponding author
- Leone, Stephen R.
- ORCID
- Venue
- Science
- Published
- 2017-04-07
- Volume
- 356
- Issue
- 6333
- Pages
- 54-59
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W2604515236
- Cited by
- 338
- References
- 63
- Citations by year
- 2026: 21 · 2025: 21 · 2024: 31 · 2023: 30 · 2022: 38 · 2021: 51 · 2020: 51 · 2019: 40 · 2018: 42 · 2017: 12
- FWCI
- 19.46
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Science (publishedVersion)
- PubMed (publishedVersion)
- eScholarship (California Digital Library) (submittedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- Funders
- National Science Foundation (award299191, EEC-0310717)
- U.S. Department of Energy (award299187, DE-AC02-05CH11231, award302135, DE-AC02-76SF00515)
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Laser-Matter Interactions and Applications
- Physical Sciences › Physics and Astronomy › Radiation › X-ray Spectroscopy and Fluorescence Analysis
- Physical Sciences › Physics and Astronomy › Radiation › Advanced X-ray Imaging Techniques
- Keywords
- electrocyclic ring opening, 1,3-cyclohexadiene, valence electronic structure, carbon K-edge, nonadiabatic relaxation, femtosecond dynamics
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