4.8 Article

Revealing electronic state-switching at conical intersections in alkyl iodides by ultrafast XUV transient absorption spectroscopy

Journal

NATURE COMMUNICATIONS
Volume 11, Issue 1, Pages -

Publisher

NATURE PUBLISHING GROUP
DOI: 10.1038/s41467-020-17745-w

Keywords

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Funding

  1. National Science Foundation [CHE-1361226, CHE-1660417]
  2. U.S. Army Research Office [W911NF-14-1-0383]
  3. U.S. Department of Energy under the Gas Phase Chemical Physics Program [DE-AC02-05CH11231]
  4. European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement [842539]
  5. Funai Overseas Scholarship
  6. Miller Institute for Basic Research in Science, University of California Berkeley
  7. Marie Curie Actions (MSCA) [842539] Funding Source: Marie Curie Actions (MSCA)

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Conical intersections between electronic states often dictate the chemistry of photoexcited molecules. Recently developed sources of ultrashort extreme ultraviolet (XUV) pulses tuned to element-specific transitions in molecules allow for the unambiguous detection of electronic state-switching at a conical intersection. Here, the fragmentation of photoexcited iso-propyl iodide and tert-butyl iodide molecules (i-C3H7I and t-C4H9I) through a conical intersection between (3)Q(0)/(1)Q(1) spin-orbit states is revealed by ultrafast XUV transient absorption measuring iodine 4d core-to-valence transitions. The electronic state-sensitivity of the technique allows for a complete mapping of molecular dissociation from photoexcitation to photoproducts. In both molecules, the sub-100 fs transfer of a photoexcited wave packet from the (3)Q(0) state into the (1)Q(1) state at the conical intersection is captured. The results show how differences in the electronic state-switching of the wave packet in i-C3H7I and t-C4H9I directly lead to differences in the photoproduct branching ratio of the two systems. The reaction trajectories of photoexcited molecules may involve transitions through conical intersections, which are ubiquitous in nature but challenging to characterize. Here the authors provide a complete mapping of molecular dissociation of two model alkyl halides by ultrafast XUV transient absorption.

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