Coherent wavepackets in the Fenna-Matthews-Olson complex are robust to excitonic-structure perturbations caused by mutagenesis.
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| 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. | 
| Year of Publication | :  2018 | 
| Journal | :  Nature chemistry | 
| Volume | :  10 | 
| Issue | :  2 | 
| Number of Pages | :  177-183 | 
| ISSN Number | :  1755-4330 | 
| URL | :  http://dx.doi.org/10.1038/nchem.2910 | 
| DOI | :  10.1038/nchem.2910 | 
| Short Title | :  Nat Chem | 
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