Catching and tracking light: following the excitations in the Fenna-Matthews-Olson complex

Peak oscillations in the FMO complex calculated using GPU-HEOM
The animation shows how peaks in the 2d echo-spectra are oscillation and changing for various delay times. For a full explanation, see Modelling of Oscillations in Two-Dimensional Echo-Spectra of the Fenna-Matthews-Olson Complex by B.Hein, C. Kreisbeck, T. Kramer, M. Rodríguez, New J. of Phys., 14, 023018 (2012), open access.

Efficient and fast transport of electric current is a basic requirement for the functioning of nanodevices and biological systems. A neat example is the energy-transport of a light-induced excitation in the Fenna-Matthews-Olson complex of green sulfur bacteria. This process has been elucidated by pump-probe spectroscopy. The resulting spectra contain an enormous amount of information about the couplings of the different pigments and the pathways taken by the excitation. The basic guide to a 2d echo-spectrum is as follows:
You can find peaks of high intensity along the diagonal line which are roughly representing a more common absorption spectrum.  If you delay the pump and probe pulses by several picoseconds, you will find a new set of peaks at a horizontal axis which indicates that energy of the excitation gets redistributed and the system relaxes and transfers part of the energy to vibrational motion. This process is nicely visible in the spectra recorded by Brixner et al.
A lot of excitement and activity on photosynthetic complexes was triggered by experiments of Engel et al showing that besides the relaxation process also periodic oscillations are visible in the oscillations for more than a picosecond.

What is causing the oscillations in the peak amplitudes of 2d echo-spectra in the Fenna-Matthews Olson complex?

A purely classical transport picture should not show such oscillations and the excitation instead hops around the complex without interference. Could the observed oscillations point to a different transport mechanism, possibly related to the quantum-mechanical simultaneous superposition of several transport paths?

The initial answer from the theoretical side was no, since within simplified models the thermalization occurs fast and without oscillations. It turned out that the simple calculations are a bit too simplistic to describe the system accurately and exact solutions are required. But exact solutions (even for simple models) are difficult to obtain. Known exact methods such as DMRG work only reliable at very low temperatures (-273 C), which are not directly applicable to biological systems. Other schemes use the famous path integrals but are too slow to calculate the pump-probe signals.

Our contribution to the field is to provide an exact computation of the 2d echo-spectra at the relevant temperatures and to see the difference to the simpler models in order to quantify how much coherence is preserved. From the method-development the computational challenge is to speed-up the calculations several hundred times in order to get results within days of computational run-time. We did achieve this by developing a method which we call GPU-hierarchical equations of motion (GPU-HEOM). The hierarchical equations of motions are a nice scheme to propagate a density matrix under consideration of non-Markovian effects and strong couplings to the environment. The HEOM scheme was developed by Kubo, Tanimura, and Ishizaki (Prof. Tanimura has posted some material on HEOM here).

However, the original computational method suffers from the same problems as path-integral calculations and is rather slow (though the HEOM method can be made faster and applied to electronic systems by using smart filtering as done by Prof. YiJing Yan). The GPU part in GPU-HEOM stands for Graphics Processing Units. Using our GPU adoption of the hierarchical equations (see details in Kreisbeck et al[JCTC, 7, 2166 (2011)] ) allowed us to cut down computational times dramatically and made it possible to perform a systematic study of the oscillations and the influence of temperature and disorder in our recent article Hein et al [New J. of Phys., 14, 023018 (2012), open access] .

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