Coherent electron hole dynamics near a conical intersection

Phys Rev Lett. 2014 Sep 12;113(11):113003. doi: 10.1103/PhysRevLett.113.113003. Epub 2014 Sep 12.

Abstract

The coherent evolution of an electron hole in a photoionized molecule represents an unexplored facet of charge transfer phenomena occurring in complex systems. Using ultrafast extreme ultraviolet spectroscopy, we investigate the real-time dynamics of an electron hole wave packet created near a conical intersection in CO_{2}. We resolve the oscillation of the electron hole density between σ and π character, driven by the coupled bending and asymmetric stretch vibrations of the molecule. We also quantify the mixing between electron hole configurations and find that the wave packet coherence diminishes with time due to thermal dephasing.

Publication types

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

MeSH terms

  • Carbon Dioxide / chemistry*
  • Electrons*
  • Models, Chemical*
  • Quantum Theory

Substances

  • Carbon Dioxide