Disordered Photosynthetic Aggregates Can Host Functional Vibronic Couplings At Room Temperature

TL;DR

This study demonstrates that disordered photosynthetic aggregates can sustain functional vibronic couplings at room temperature, revealing insights into energy transfer mechanisms in natural and artificial systems.

Contribution

It provides experimental evidence of vibronic couplings in large, disordered photosynthetic aggregates at physiological temperatures, highlighting the role of disorder in facilitating these interactions.

Findings

Vibronic couplings are present at room temperature in photosynthetic aggregates.

Disorder enhances Qx-Qy vibronic mixing across the Q band.

Artificial porphyrin nanotubes exhibit similar vibronic features as natural systems.

Abstract

Photosynthesis relies on a network of chlorophyll-like molecules which together lead to efficient long-range energy funneling. Evidence at cryogenic temperatures suggests that mechanistic details of energy/charge transfer must invoke delocalized vibronic states. Whether these survive at physiological temperature in large photosynthetic aggregates is an open question. Parallel research on artificial templates has relied on cyanines which are unlike chlorophylls. We report two-dimensional electronic spectra of porphyrin nanotubes where we selectively probe mixed Qx-Qy states through polarization control. Early time cross-peaks, their rapid broadening and survival of anisotropic Qx-Qy quantum beats conclusively demonstrate that overlapping vibrational-electronic bands of photosynthetic aggregates indeed host functional vibronic couplings at room temperature. Calculations reveal that disorder is the vital ingredient that dramatically enhances Qx-Qy vibronic mixing across the entire Q band. The parameter regime where energetic disorder is of the order of dense Raman-active vibrations with weak reorganization energies may be the key design principle.