4.8 Article

Diffractive Imaging of Conical Intersections Amplified by Resonant Infrared Fields

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 34, Pages 13806-13815

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c06068

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Funding

  1. Chemical Sciences, Geosciences, and Bio-Sciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy [DE-SC0019484]
  2. Alexander von Humboldt foundation through the Feodor Lynen program

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Research demonstrates that using a resonant infrared field at conical intersections can enhance coherence features of photoisomerization reactions and bring signals of conical intersections above the detection threshold.
The fate of virtually all photochemical reactions is determined by conical intersections. These are energetically degenerate regions of molecular potential energy surfaces that strongly couple electronic states, thereby enabling fast relaxation channels. Their direct spectroscopic detection relies on weak features that are often buried beneath stronger, less interesting contributions. For azobenzene photoisomerization, a textbook photochemical reaction, we demonstrate how a resonant infrared field can be employed during the conical intersection passage to significantly enhance its coherence signatures in time-resolved X-ray diffraction while leaving the product yield intact. This transition-state amplification holds promise to bring signals of conical intersections above the detection threshold.

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