Excited state coherent dynamics in light-harvesting complexes from photosynthetic marine algae

We explore coherence dynamics in light-harvesting complexes and their interactions with other electronic states and vibrational modes. This is achieved by utilizing a two-colour four-wave mixing spectroscopy to excite and analyse a specific coherence pathway in the phycocyanin-645 (PC645) light-harvesting complex. We observe the dephasing rate increase as a function of temperature and oscillations in the signal intensity as a function of waiting time which reveals coherent excitation of pathways not directly resonant with the laser pulses. This coherent excitation of non-resonant electronic states implies strong coupling to phonon modes, which is necessary if coherent energy transfer between non-resonant states is to play any role in photosynthetic energy transfer.