Two-dimensional electronic spectroscopy using incoherent light: theoretical analysis

J Phys Chem A. 2013 Jul 25;117(29):5926-54. doi: 10.1021/jp310477y. Epub 2012 Dec 10.

Abstract

Electronic energy transfer in photosynthesis occurs over a range of time scales and under a variety of intermolecular coupling conditions. Recent work has shown that electronic coupling between chromophores can lead to coherent oscillations in two-dimensional electronic spectroscopy measurements of pigment-protein complexes measured with femtosecond laser pulses. A persistent issue in the field is to reconcile the results of measurements performed using femtosecond laser pulses with physiological illumination conditions. Noisy-light spectroscopy can begin to address this question. In this work we present the theoretical analysis of incoherent two-dimensional electronic spectroscopy, I((4)) 2D ES. Simulations reveal diagonal peaks, cross peaks, and coherent oscillations similar to those observed in femtosecond two-dimensional electronic spectroscopy experiments. The results also expose fundamental differences between the femtosecond-pulse and noisy-light techniques; the differences lead to new challenges and new opportunities.

Publication types

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

MeSH terms

  • Color
  • Electron Transport
  • Electrons*
  • Light
  • Models, Molecular
  • Molecular Conformation
  • Photosynthesis
  • Spectrum Analysis*
  • Time Factors