Conical intersection dynamics in NO2 probed by homodyne high-harmonic spectroscopy

Science. 2011 Oct 14;334(6053):208-12. doi: 10.1126/science.1208664.

Abstract

Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occur in nitrogen dioxide when a photoexcited wave packet crosses a conical intersection. At longer delays, we observe the onset of statistical dissociation dynamics. The present results demonstrate that high-harmonic spectroscopy could become a powerful tool to highlight electronic dynamics occurring along nonadiabatic chemical reaction pathways.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.