Catching Conical Intersections in the Act: Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals
Open accessAbstract
Conical intersections (CIs) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CIs have not been directly observed yet and the experimental evidence is being inferred from fast reaction rates and some vibrational signatures. We show that short x-ray (rather than optical) pulses can directly detect the passage through a CI with the adequate temporal and spectral sensitivity. The technique is based on a coherent Raman process that employs a composite femtosecond or attosecond x-ray pulse to detect the electronic coherences (rather than populations) that are generated as the system passes through the CI.
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At conical intersections, the energy splitting of the electronic states involved in the coherence can be read from the Raman shift, and the coherent oscillation period reveals this time-dependent level splitting averaged over the nuclear wavepacket.
“At conical intersections, the energy splitting of the electronic states involved in the coherence can be read from the Raman shift and the coherent oscillation period reveals this time-dependent level splitting averaged over the nuclear wavepacket [43].”
From Roadmap of ultrafast x-ray atomic and molecular physics (2018) · cites this paper as [43]
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Cites
Berry phase effects on electronic properties
Xiao, D., Chang, M.-C., & Niu, Q. (2010) · Reviews of Modern Physics · doi:10.1103/revmodphys.82.1959 · Cited by 5,277 · see citing works
Bright Coherent Ultrahigh Harmonics in the keV X-ray Regime from Mid-Infrared Femtosecond Lasers
Popmintchev, T., Chen, M.-C., Popmintchev, D., Arpin, P., Brown, S., Ališauskas, S., Andriukaitis, G., Balčiunas, T., Mücke, O. D., Pugzlys, A., et al. (2012) · Science · doi:10.1126/science.1218497 · Cited by 1,830 · see citing works
Domcke, W., Yarkony, D. R., & Köppel, H. (2004) · Advanced series in physical chemistry · doi:10.1142/5406 · Cited by 1,345 · see citing works
Introduction to Quantum Mechanics: A Time-Dependent Perspective
Tannor, D. J. (2006) · Cited by 1,027 · see citing works
Vibrational dynamics of liquids and solids investigated by picosecond light pulses
Laubereau, A., & Kaiser, W. (1978) · Reviews of Modern Physics · doi:10.1103/revmodphys.50.607 · Cited by 1,011 · see citing works
Conical intersection dynamics of the primary photoisomerization event in vision
Polli, D., Altoè, P., Weingart, O., Spillane, K. M., Manzoni, C., Brida, D., Tomasello, G., Orlandi, G., Kukura, P., Mathies, R. A., et al. (2010) · Nature · doi:10.1038/nature09346 · Cited by 948 · see citing works
Sobolewski, A. L., Domcke, W., Dedonder‐Lardeux, C., & Jouvet, C. M. R. (2002) · Physical Chemistry Chemical Physics · doi:10.1039/b110941n · Cited by 916 · see citing works
Femtosecond Stimulated Raman Spectroscopy
Kukura, P., McCamant, D. W., & Mathies, R. A. (2006) · Annual Review of Physical Chemistry · doi:10.1146/annurev.physchem.58.032806.104456 · Cited by 638 · see citing works
The attosecond nonlinear optics of bright coherent X-ray generation
Popmintchev, T., Chen, M.-C., Arpin, P. C., Murnane, M. M., & Kapteyn, H. C. (2010) · Nature Photonics · doi:10.1038/nphoton.2010.256 · Cited by 612 · see citing works
Barbatti, M., Granucci, G., Persico, M., Ruckenbauer, M., Vazdar, M., Eckert‐Maksić, M., & Lischka, H. (2006) · Journal of Photochemistry and Photobiology A Chemistry · doi:10.1016/j.jphotochem.2006.12.008 · Cited by 500 · see citing works
Coherent Raman spectro-imaging with laser frequency combs
Ideguchi, T., Holzner, S., Bernhardt, B., Guelachvili, G., Picqué, N., & Hänsch, T. W. (2013) · Nature · doi:10.1038/nature12607 · Cited by 475 · see citing works
Raab, A., Worth, G. A., Meyer, H., et al. (1999) · The Journal of Chemical Physics · doi:10.1063/1.478061 · Cited by 471 · see citing works
Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases
Barbatti, M., Aquino, A. J. A., Szymczak, J. J., Nachtigallová, D., Hobza, P., & Lischka, H. (2010) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1014982107 · Cited by 442 · see citing works
Achieving few-femtosecond time-sorting at hard X-ray free-electron lasers
Harmand, M., Coffee, R., Bionta, M. R., Chollet, M., French, D., Zhu, D., Fritz, D., Lemke, H. T., Medvedev, N. A., Ziaja, B., et al. (2013) · Nature Photonics · doi:10.1038/nphoton.2013.11 · Cited by 376 · see citing works
Four-wave mixing experiments with extreme ultraviolet transient gratings
Bencivenga, F., Cucini, R., Capotondi, F., Battistoni, A., Mincigrucci, R., Giangrisostomi, E., Gessini, A., Manfredda, M., Nikolov, I. P., Pedersoli, E., et al. (2015) · Nature · doi:10.1038/nature14341 · Cited by 250 · see citing works
Conical Intersections - Electronic Structure, Dynamics and Spectroscopy
(2004) · Advanced series in physical chemistry · doi:10.1142/9789812565464 · Cited by 231 · see citing works
Coherent pulse synthesis: towards sub-cycle optical waveforms
Manzoni, C., Mücke, O. D., Cirmi, G., Fang, S., Moses, J., Huang, S., Hong, K.-H., Cerullo, G., & Käertner, F. X. (2015) · Laser & Photonics Review · doi:10.1002/lpor.201400181 · Cited by 225 · see citing works
Ultrafast X-ray pulse characterization at free-electron lasers
Grguraš, I., Maier, A. R., Behrens, C., Mazza, T., Kelly, T. J., Radcliffe, P., Düsterer, S., Kazansky, A. K., Kabachnik, N. M., Tschentscher, T., et al. (2012) · Nature Photonics · doi:10.1038/nphoton.2012.276 · Cited by 210 · see citing works
Oliver, T. A. A., Lewis, N. H. C., & Fleming, G. R. (2014) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1409207111 · Cited by 205 · see citing works
Bostedt, C., Bozek, J. D., Bucksbaum, P. H., Coffee, R., Hastings, J. B., Huang, Z., Lee, R. W., Schorb, S., Corlett, J. N., Denes, P., et al. (2013) · Journal of Physics B Atomic Molecular and Optical Physics · doi:10.1088/0953-4075/46/16/164003 · Cited by 178 · see citing works
Ultrafast X-ray Auger probing of photoexcited molecular dynamics
McFarland, B. K., Farrell, J. P., Miyabe, S., Tarantelli, F., Aguilar, A., Berrah, N., Bostedt, C., Bozek, J. D., Bucksbaum, P. H., Castagna, J. C., et al. (2014) · Nature Communications · doi:10.1038/ncomms5235 · Cited by 161 · see citing works
Femtosecond time-resolved Raman spectroscopy using stimulated Raman scattering
Yoshizawa, M., & Kurosawa, M. (1999) · Physical Review A · doi:10.1103/physreva.61.013808 · Cited by 154 · see citing works
Stimulated Electronic X-Ray Raman Scattering
Weninger, C., Purvis, M., Ryan, D., London, R. A., Bozek, J. D., Bostedt, C., Graf, A., Brown, G., Rocca, J. J., & Rohringer, N. (2013) · Physical Review Letters · doi:10.1103/physrevlett.111.233902 · Cited by 148 · see citing works
Ultrafast internal conversion in ethylene. I. The excited state lifetime
Tao, H., Allison, T. K., Wright, T. W., et al. (2011) · The Journal of Chemical Physics · doi:10.1063/1.3604007 · Cited by 141 · see citing works
Single-shot detection of bacterial endospores via coherent Raman spectroscopy
Pestov, D., Wang, X., Ariunbold, G. O., Murawski, R. K., Sautenkov, V. A., Dogariu, A., Sokolov, A. V., & Scully, M. O. (2008) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0710427105 · Cited by 138 · see citing works
Horio, T., Fuji, T., Suzuki, Y., et al. (2009) · Journal of the American Chemical Society · doi:10.1021/ja904780b · Cited by 127 · see citing works
Optical antennas focus in on biology
Parajo, M. F. G. (2008) · Nature Photonics · doi:10.1038/nphoton.2008.37 · Cited by 114 · see citing works
Miller, J. D., Roy, S., Slipchenko, M. N., et al. (2011) · Optics Express · doi:10.1364/oe.19.015627 · Cited by 109 · see citing works
Ding, Y., Huang, Z., Ratner, D. F., et al. (2009) · Physical Review Special Topics - Accelerators and Beams · doi:10.1103/physrevstab.12.060703 · Cited by 101 · see citing works
Helml, W., Maier, A. R., Schweinberger, W., Grguraš, I., Radcliffe, P., Doumy, G., Roedig, C., Gagnon, J., Messerschmidt, M. M., Schorb, S., et al. (2014) · Nature Photonics · doi:10.1038/nphoton.2014.278 · Cited by 95 · see citing works
Ab initio nonadiabatic quantum dynamics of cyclohexadiene/hexatriene ultrafast photoisomerization
Tamura, H., Nanbu, S., Ishida, T., & Nakamura, H. (2006) · The Journal of Chemical Physics · doi:10.1063/1.2171688 · Cited by 90 · see citing works
Ultrafast Nonlinear Optical Signals Viewed from the Molecule’s Perspective
Mukamel, S., & Rahav, S. (2010) · Advances in atomic, molecular, and optical physics · doi:10.1016/s1049-250x(10)59006-2 · Cited by 87 · see citing works
Self-citationSubstituent Effects on Dynamics at Conical Intersections: α,β-Enones
Lee, A. M. D., Coe, J. D., Ullrich, S., et al. (2007) · The Journal of Physical Chemistry A · doi:10.1021/jp074622j · Cited by 85 · see citing works
Optimal control theory – closing the gap between theory and experiment
von den Hoff, P., Thallmair, S., Kowalewski, M., Siemering, R., & de Vivie‐Riedle, R. (2012) · Physical Chemistry Chemical Physics · doi:10.1039/c2cp41838j · Cited by 74 · see citing works
Self-citationQuantum theory of (femtosecond) time-resolved stimulated Raman scattering
Sun, Z., Lu, J., Zhang, D. H., et al. (2008) · The Journal of Chemical Physics · doi:10.1063/1.2888551 · Cited by 70 · see citing works
Single-beam spectrally controlled two-dimensional Raman spectroscopy
Frostig, H., Bayer, T., Dudovich, N., Eldar, Y. C., & Silberberg, Y. R. (2015) · Nature Photonics · doi:10.1038/nphoton.2015.64 · Cited by 69 · see citing works
Rinaldi, S., Melaccio, F., Gozem, S., Fanelli, F., & Olivucci, M. (2014) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1309508111 · Cited by 66 · see citing works
Wiersma, D. A. (1994) · North-Holland eBooks · Cited by 57 · see citing works
Coherent Electron Hole Dynamics Near a Conical Intersection
Timmers, H. R., Li, Z., Shivaram, N., Santra, R., Vendrell, O., & Sandhu, A. S. (2014) · Physical Review Letters · doi:10.1103/physrevlett.113.113003 · Cited by 53 · see citing works
Fingerhut, B. P., Dorfman, K. E., & Mukamel, S. (2014) · Journal of Chemical Theory and Computation · doi:10.1021/ct401012u · Cited by 50 · see citing works
Self-citationHua, W., Oesterling, S., Biggs, J. D., Zhang, Y. A., Ando, H., de Vivie‐Riedle, R., Fingerhut, B. P., & Mukamel, S. (2015) · Structural Dynamics · doi:10.1063/1.4933007 · Cited by 48 · see citing works
Self-citationEarly Events in the Nonadiabatic Relaxation Dynamics of 4-( N , N -Dimethylamino)benzonitrile
Kochman, M. A., Tajti, A., Morrison, C. A., et al. (2015) · Journal of Chemical Theory and Computation · doi:10.1021/ct5010609 · Cited by 33 · see citing works
Generation of stable subfemtosecond hard x-ray pulses with optimized nonlinear bunch compression
Huang, S., Ding, Y., Huang, Z., et al. (2014) · Physical Review Special Topics - Accelerators and Beams · doi:10.1103/physrevstab.17.120703 · Cited by 22 · see citing works
Kowalewski, M., & Mukamel, S. (2015) · The Journal of Chemical Physics · doi:10.1063/1.4927475 · Cited by 20 · see citing works
Self-citationDetecting electronic coherence by multidimensional broadband stimulated x-ray Raman signals
Dorfman, K. E., Bennett, K., & Mukamel, S. (2015) · Physical Review A · doi:10.1103/physreva.92.023826 · Cited by 19 · see citing works
Self-citationShort-Time Dynamics at a Conical Intersection in High-Harmonic Spectroscopy
Patchkovskii, S., & Schuurman, M. S. (2014) · The Journal of Physical Chemistry A · doi:10.1021/jp5090444 · Cited by 13 · see citing works
Transient Impulsive Electronic Raman Redistribution
Miyabe, S., & Bucksbaum, P. H. (2015) · Physical Review Letters · doi:10.1103/physrevlett.114.143005 · Cited by 12 · see citing works
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Research works printed but not linked: 1
- [6]M. Barbatti, A. J. A. Aquino, J. J. Szymczak, D. Nachtigallov´ a, P. Hobza, and H. Lischka, Proc. Natl. Acad. Sci. USA 107 , 21453 (2010).
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Roadmap of ultrafast x-ray atomic and molecular physics
Young, L., Ueda, K., Gühr, M., Bucksbaum, P. H., Simon, M., Mukamel, S., Rohringer, N., Prince, K. C., Masciovecchio, C., Meyer, M., et al. (2018) · Journal of Physics B: Atomic, Molecular and Optical Physics · doi:10.1088/1361-6455/aa9735 · Cited by 337 · see citing works
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Self-citation
- Authors
- Kowalewski, M., Bennett, K., Dorfman, K. E., & Mukamel, S.
- Affiliations
- University of California, Irvine (US)
- Venue
- Physical Review Letters
- Publisher
- American Physical Society (APS)
- Published
- 2015-11-05
- Volume
- 115
- Issue
- 19
- Pages
- 193003-193003
- ISSN
- 0031-9007 (ISSN-L)
- 1079-7114
- OpenAlex
- W2180431983
- Cited by
- 165
- References
- 47
- Citations by year
- 2026: 6 · 2025: 13 · 2024: 16 · 2023: 18 · 2022: 23 · 2021: 22 · 2020: 14 · 2019: 13 · 2018: 10 · 2017: 15 · 2016: 14 · 2015: 1
- FWCI
- 6.78
- Type
- journal article
- Language
- en
- Open access
- green
- arxiv.org
- Licence
- Locations
- Physical Review Letters (publishedVersion)
- PubMed (publishedVersion)
- arXiv (Cornell University) (submittedVersion)
- eScholarship (California Digital Library) (submittedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- arXiv (Cornell University)
- Funders
- U.S. Department of Energy (DE-FG02-04ER15571)
- National Science Foundation (CHE-1361516)
- Alexander von Humboldt-Stiftung
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Laser-Matter Interactions and Applications
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Keywords
- conical intersections, stimulated Raman scattering, X-ray pulses, attosecond pulses, femtosecond pulses, coherent Raman spectroscopy, photochemical dynamics, molecular photophysics
- MeSH terms
- Computer Simulation, Models, Theoretical, Photochemistry, Spectrum Analysis, Raman, Photochemical Processes
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