We revise the interpretation of coherence signals in photosynthetic systems and clarify what they tell us about light harvesting.

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales $<$100 fs. Today’s understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds. This orthodox picture of incoherent energy transfer between clusters of a few pigments sharing delocalized excitons has been challenged by ultrafast optical spectroscopy experiments with the Fenna–Matthews–Olson protein, in which interference oscillatory signals up to 1.5 ps were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidence of any long-lived electronic quantum coherence, but confirm the orthodox view of rapidly decaying electronic quantum coherence on a timescale of 60 fs. Our results can be considered as generic and give no hint that electronic quantum coherence plays any biofunctional role in real photoactive biomolecular complexes. Because in this structurally well-defined protein the distances between bacteriochlorophylls are comparable to those of other light-harvesting complexes, we anticipate that this finding is general and directly applies to even larger photoactive biomolecular complexes. Significance We have revisited the 2D spectroscopy of the excitation energy transfer in the Fenna–Matthews–Olson (FMO) protein. Based on 2D spectroscopic signatures, the energy transfer dynamics in the FMO protein has been argued to be supported by long-lived electronic quantum coherence on timescales up to 1.5 ps. In contrast, our analysis, based on experimental data and confirmed by theoretical calculations, shows that the electronic decoherence occurs within 60 fs, in agreement with typical dephasing times in systems under these conditions. Given the relatively well-defined structure of the FMO protein, and comparative couplings between chlorophylls to other photosynthetic systems, the observed extremely fast decoherence should be viewed as general, bringing to question any significant quantum coherent transport contributions to photosynthesis.

Two-dimensional infrared photon-echo measurements of the OH stretching vibration in liquid H₂O are performed at various temperatures. Spectral diffusion and resonant energy transfer occur on a time scale much shorter than the average hydrogen bond lifetime of ≈1 ps. Room temperature measurements show a loss of frequency and, thus, structural correlations on a 50-fs time scale. Weakly hydrogen-bonded OH stretching oscillators absorbing at high frequencies undergo slower spectral diffusion than strongly bonded oscillators. In the temperature range from 340 to 274 K, the loss in memory slows down with decreasing temperature. At 274 K, frequency correlations in the OH stretch vibration persist beyond ≈200 fs, pointing to a reduction in dephasing by librational excitations. Polarization-resolved pump-probe studies give a resonant intermolecular energy transfer time of 80 fs, which is unaffected by temperature. At low temperature, structural correlations persist longer than the energy transfer time, suggesting a delocalization of OH stretching excitations over several water molecules.

Femtosecond electron diffraction (FED) has the potential to directly observe transition state processes. The relevant motions for this barrier-crossing event occur on the hundred femtosecond time-scale. Recent advances in the development of high-flux electron pulse sources with the required time resolution and sensitivity to capture barrier-crossing processes are described in the context of attaining atomic level details of such structural dynamics—seeing chemical events as they occur. Initial work focused on the ordered-to-disordered phase transition of Al under strong driving conditions for which melting takes on nm or molecular scale dimensions. This work has been extended to Au, which clearly shows a separation in time-scales for lattice heating and melting. It also demonstrates that superheated face-centred cubic (FCC) metals melt through thermal mechanisms involving homogeneous nucleation to propagate the disordering process. A new concept exploiting electron–electron correlation is introduced for pulse characterization and determination oft=0 to within 100 fs as well as for spatial manipulation of the electron beam. Laser-based methods are shown to provide further improvements in time resolution with respect to pulse characterization, absolutet=0 determination, and the potential for electron acceleration to energies optimal for time-resolved diffraction.

The excitation of a high density of carriers in semiconductors can induce an order-to-disorder phase transition due to changes in the potential-energy landscape of the lattice. We report the first direct resolution of the structural details of this phenomenon in freestanding films of polycrystalline and (001)-oriented crystalline Si, using 200-fs electron pulses. At excitation levels greater than $\sim 6\%$ of the valence electron density, the crystalline structure of the lattice is lost in $<500\mathrm{fs}$, a time scale indicative of an electronically driven phase transition. We find that the relaxation process along the modified potential is not inertial but rather involves multiple scattering towards the disordered state.