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

Abstract

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, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF ₃ I 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:

Yang, Jie  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-5115-2413"

Zhu, Xiaolei  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-7825-4815"

Wolf, Thomas J. A.  ^[3];

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• Search DOE PAGES for ORCID "0000-0002-0641-1279"

Li, Zheng  ^[4];

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• Search DOE PAGES for ORCID "0000-0002-5483-9149"

Nunes, J. Pedro F.  ^[5];

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• Search DOE PAGES for ORCID "0000-0003-0670-6023"

Coffee, Ryan  ^[6];

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• Search DOE PAGES for ORCID "0000-0002-2619-8823"

Cryan, James P. ^[3]; Gühr, Markus ^[7]; Hegazy, Kareem  ^[8];

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• Search DOE PAGES for ORCID "0000-0001-6043-188X"

Heinz, Tony F.  ^[9];

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• Search DOE PAGES for ORCID "0000-0003-1365-9464"

Jobe, Keith ^[10]; Li, Renkai  ^[10];

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• Search DOE PAGES for ORCID "0000-0002-3163-5506"

Shen, Xiaozhe  ^[10];

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• Search DOE PAGES for ORCID "0000-0001-8423-1022"

Veccione, Theodore ^[10]; Weathersby, Stephen ^[10]; Wilkin, Kyle J. ^[11]; Yoneda, Charles ^[10]; Zheng, Qiang ^[10]; Martinez, Todd J.  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-4798-8947"

Centurion, Martin ^[11] more »; Wang, Xijie ^[10] « less

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+ Show Author Affiliations

1. SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
2. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Department of Chemistry, Stanford University, Stanford, CA, USA.
3. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
4. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany., Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany.
5. Department of Chemistry, University of York, Heslington, York, UK.
6. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Department of Physics, Stanford University, Stanford, CA, USA.
7. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Institut für Physik und Astronomie, Universität Potsdam, Potsdam, Germany.
8. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Department of Physics, Stanford University, Stanford, CA, USA.
9. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA., Department of Applied Physics, Stanford University, Stanford, CA, USA.
10. SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
11. Department of Physics and Astronomy, University of Nebraska–Lincoln, Lincoln, NE, USA.

Publication Date:

Thu Jul 05 00:00:00 EDT 2018

Research Org.:

SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1459056

Alternate Identifier(s):

OSTI ID: 1461482

Grant/Contract Number:  

AC02-05-CH11231; AC02-76SF00515; SC0014170; ACI-1429830

Resource Type:

Published Article

Journal Name:

Science

Additional Journal Information:

Journal Name: Science Journal Volume: 361 Journal Issue: 6397; Journal ID: ISSN 0036-8075

Publisher:

American Association for the Advancement of Science (AAAS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY