Vibrationally coherent crossing and coupling of electronic states during internal conversion in β-carotene

Phys Rev Lett. 2014 May 16;112(19):198302. doi: 10.1103/PhysRevLett.112.198302. Epub 2014 May 15.

Abstract

Coupling of nuclear and electronic degrees of freedom mediates energy flow in molecules after optical excitation. The associated coherent dynamics in polyatomic systems, however, remain experimentally unexplored. Here, we combined transient absorption spectroscopy with electronic population control to reveal nuclear wave packet dynamics during the S2 → S1 internal conversion in β-carotene. We show that passage through a conical intersection is vibrationally coherent and thereby provides direct feedback on the role of different vibrational coordinates in the breakdown of the Born-Oppenheimer approximation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Photochemical Processes
  • Spectrum Analysis, Raman / methods
  • Thermodynamics
  • Tomography, Optical Coherence / methods*
  • Vibration
  • beta Carotene / chemistry*

Substances

  • beta Carotene