Coherent wavepackets in the Fenna-Matthews-Olson complex are robust to excitonic-structure perturbations caused by mutagenesis

Nat Chem. 2018 Feb;10(2):177-183. doi: 10.1038/nchem.2910. Epub 2018 Jan 15.

Abstract

Femtosecond pulsed excitation of light-harvesting complexes creates oscillatory features in their response. This phenomenon has inspired a large body of work aimed at uncovering the origin of the coherent beatings and possible implications for function. Here we exploit site-directed mutagenesis to change the excitonic level structure in Fenna-Matthews-Olson (FMO) complexes and compare the coherences using broadband pump-probe spectroscopy. Our experiments detect two oscillation frequencies with dephasing on a picosecond timescale-both at 77 K and at room temperature. By studying these coherences with selective excitation pump-probe experiments, where pump excitation is in resonance only with the lowest excitonic state, we show that the key contributions to these oscillations stem from ground-state vibrational wavepackets. These experiments explicitly show that the coherences-although in the ground electronic state-can be probed at the absorption resonances of other bacteriochlorophyll molecules because of delocalization of the electronic excitation over several chromophores.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bacteriochlorophyll A / chemistry
  • Bacteriochlorophyll A / genetics*
  • Light-Harvesting Protein Complexes / chemistry
  • Light-Harvesting Protein Complexes / genetics*
  • Models, Molecular
  • Mutagenesis, Site-Directed*
  • Quantum Theory

Substances

  • Bacteriochlorophyll A
  • Light-Harvesting Protein Complexes