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Title: Imaging CF 3I conical intersection and photodissociation dynamics with ultrafast electron diffraction

Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here in this paper, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF 3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF 3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [4] ; ORCiD logo [5] ; ORCiD logo [6] ;  [3] ;  [7] ; ORCiD logo [8] ; ORCiD logo [9] ;  [10] ; ORCiD logo [10] ; ORCiD logo [10] ;  [10] ;  [10] ;  [11] ;  [10] ;  [10] ; ORCiD logo [2] ;  [11] more »;  [10] « less
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Stanford Univ., CA (United States). Dept. of Chemistry
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science; Max Planck Inst. for the Structure and Dynamics of Matter, Hamburg (Germany)
  5. Univ. of York (United Kingdom). Dept. of Chemistry
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Stanford Univ., CA (United States). Dept. of Physics
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Univ. of Potsdam (Germany). Inst. fur Physik und Astronomie
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Stanford Univ., CA (United States). Dept. of Physics
  9. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Stanford Univ., CA (United States). Dept. of Applied Physics
  10. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  11. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy
Publication Date:
Grant/Contract Number:
ACI-1429830; AC02-05-CH11231; AC02-76SF00515; SC0014170
Type:
Published Article
Journal Name:
Science
Additional Journal Information:
Journal Volume: 361; Journal Issue: 6397; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1459056
Alternate Identifier(s):
OSTI ID: 1461482

Yang, Jie, Zhu, Xiaolei, Wolf, Thomas J. A., Li, Zheng, Nunes, J. Pedro F., Coffee, Ryan, Cryan, James P., Guhr, Markus, Hegazy, Kareem, Heinz, Tony F., Jobe, Keith, Li, Renkai, Shen, Xiaozhe, Veccione, Theodore, Weathersby, Stephen, Wilkin, Kyle J., Yoneda, Charles, Zheng, Qiang, Martinez, Todd J., Centurion, Martin, and Wang, Xijie. Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction. United States: N. p., Web. doi:10.1126/science.aat0049.
Yang, Jie, Zhu, Xiaolei, Wolf, Thomas J. A., Li, Zheng, Nunes, J. Pedro F., Coffee, Ryan, Cryan, James P., Guhr, Markus, Hegazy, Kareem, Heinz, Tony F., Jobe, Keith, Li, Renkai, Shen, Xiaozhe, Veccione, Theodore, Weathersby, Stephen, Wilkin, Kyle J., Yoneda, Charles, Zheng, Qiang, Martinez, Todd J., Centurion, Martin, & Wang, Xijie. Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction. United States. doi:10.1126/science.aat0049.
Yang, Jie, Zhu, Xiaolei, Wolf, Thomas J. A., Li, Zheng, Nunes, J. Pedro F., Coffee, Ryan, Cryan, James P., Guhr, Markus, Hegazy, Kareem, Heinz, Tony F., Jobe, Keith, Li, Renkai, Shen, Xiaozhe, Veccione, Theodore, Weathersby, Stephen, Wilkin, Kyle J., Yoneda, Charles, Zheng, Qiang, Martinez, Todd J., Centurion, Martin, and Wang, Xijie. 2018. "Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction". United States. doi:10.1126/science.aat0049.
@article{osti_1459056,
title = {Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction},
author = {Yang, Jie and Zhu, Xiaolei and Wolf, Thomas J. A. and Li, Zheng and Nunes, J. Pedro F. and Coffee, Ryan and Cryan, James P. and Guhr, Markus and Hegazy, Kareem and Heinz, Tony F. and Jobe, Keith and Li, Renkai and Shen, Xiaozhe and Veccione, Theodore and Weathersby, Stephen and Wilkin, Kyle J. and Yoneda, Charles and Zheng, Qiang and Martinez, Todd J. and Centurion, Martin and Wang, Xijie},
abstractNote = {Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here in this paper, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.},
doi = {10.1126/science.aat0049},
journal = {Science},
number = 6397,
volume = 361,
place = {United States},
year = {2018},
month = {7}
}

Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a