In the previous post I described some of the computational challenges for modeling energy transfer in the light harvesting complex II (LHCII) found in spinach. Here, I discuss the results we have obtained for the dynamics and choreography of excitonic energy transfer through the chlorophyll network. Compared to the Fenna-Matthews-Olson complex, LHCII has twice as many chlorophylls per monomeric unit (labeled 601-614 with chlorophyll a and b types).
Previous studies of exciton dynamics had to stick to simple exponential decay models based on either Redfield or Förster theory for describing the transfer from the Chl b to the Chl a sites. The results are not satisfying and conclusive, since depending on the method chosen the transfer time differs widely (tens of picoseconds vs picoseconds!).

To resolve the discrepancies between the various approximate methods requires a more accurate approach. With the accelerated HEOM at hand, we revisited the problem and calculated the transfer rates. We find slower rates than given by the Redfield expressions. A combined Förster-Redfield description is possible in hindsight by using HEOM to identify a suitable cut-off parameter (Mcr=30/cm in this specific case).

Since the energy transfer is driven by the coupling of electronic degrees of freedom to vibrational ones, it of importance to assess how the vibrational mode distribution affects the transfer. In particular it has been proposed that specifically tuned vibrational modes might promote a fast relaxation. We find no strong impact of such modes on the transfer, rather we see (independent of the detailed vibrational structure) several bottleneck states, which act as a transient reservoir for the exciton flux. The details and distribution of the bottleneck states strongly depends on the parameters of the electronic couplings and differs for the two most commonly discussed LHCII models proposed by Novoderezhkin/Marin/van Grondelle and Müh/Madjet/Renger – both are considered in the article Scalable high-performance algorithm for the simulation of exciton-dynamics. Application to the light harvesting complex II in the presence of resonant vibrational modes (collaboration of Christoph Kreisbeck, Tobias Kramer, Alan Aspuru-Guzik).
Again, the correct assignment of the bottleneck states requires to use HEOM and to look beyond the approximate rate equations.