标题： 无序光合聚集体可以在室温下容纳功能性的振动耦合 显示英文标题

标题： Disordered Photosynthetic Aggregates Can Host Functional Vibronic Couplings At Room Temperature

摘要： 光合作用依赖于一系列类似叶绿素的分子网络，这些分子共同导致高效的长距离能量收集。 低温下的证据表明，能量/电荷转移的机制细节必须涉及离域的振子态。 在生理温度下，这些态是否在大的光合聚集体中仍然存在是一个开放性问题。 对人工模板的并行研究一直依赖于与叶绿素不同的菁类染料。 我们报告了卟啉纳米管的二维电子光谱，在其中通过偏振控制选择性地探测混合的Qx-Qy态。 早期时间的交叉峰、它们的快速展宽以及各向异性Qx-Qy量子振荡的持续存在，明确证明了光合聚集体重叠的振动-电子带确实能够在室温下容纳功能性的振子耦合。 计算结果表明，无序是显著增强整个Q带中Qx-Qy振子混合的关键因素。 当能级无序与密集的拉曼活性振动相当且重组能较弱时，可能就是关键的设计原则。 显示英文摘要

摘要： 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.