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Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction.

  • Author(s): Attar, Andrew R;
  • Bhattacherjee, Aditi;
  • Pemmaraju, CD;
  • Schnorr, Kirsten;
  • Closser, Kristina D;
  • Prendergast, David;
  • Leone, Stephen R
  • et al.
Abstract

The ultrafast light-activated electrocyclic ring-opening reaction of 1,3-cyclohexadiene is a fundamental prototype of photochemical pericyclic reactions. Generally, these reactions are thought to proceed through an intermediate excited-state minimum (the so-called pericyclic minimum), which leads to isomerization via nonadiabatic relaxation to the ground state of the photoproduct. Here, we used femtosecond (fs) soft x-ray spectroscopy near the carbon K-edge (~284 electron volts) on a tabletop apparatus to directly reveal the valence electronic structure of this transient intermediate state. The core-to-valence spectroscopic signature of the pericyclic minimum observed in the experiment was characterized, in combination with time-dependent density functional theory calculations, to reveal overlap and mixing of the frontier valence orbital energy levels. We show that this transient valence electronic structure arises within 60 ± 20 fs after ultraviolet photoexcitation and decays with a time constant of 110 ± 60 fs.

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