Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
Kavli Energy Nanoscience Institute at Berkeley, Berkeley, CA, 94720, USA.
Nat Commun. 2020 Nov 26;11(1):6011. doi: 10.1038/s41467-020-19800-y.
The importance of green light for driving natural photosynthesis has long been underappreciated, however, under the presence of strong illumination, green light actually drives photosynthesis more efficiently than red light. This green light is absorbed by mixed vibronic Q-Q states, arising from chlorophyll (Chl)-Chl interactions, although almost nothing is known about these states. Here, we employ polarization-dependent two-dimensional electronic-vibrational spectroscopy to study the origin and dynamics of the mixed vibronic Q-Q states of light-harvesting complex II. We show the states in this region dominantly arise from Chl b and demonstrate how it is possible to distinguish between the degree of vibronic Q versus Q character. We find that the dynamics for states of predominately Chl b Q versus Chl b Q character are markedly different, as excitation persists for significantly longer in the Q states and there is an oscillatory component to the Q dynamics, which is discussed. Our findings demonstrate the central role of electronic-nuclear mixing in efficient light-harvesting and the different functionalities of Chl a and Chl b.
然而,长期以来,人们一直低估绿光在驱动自然光合作用方面的重要性。在强光照下,绿光实际上比红光更有效地驱动光合作用。这种绿光被混合的振子 Q-Q 态吸收,这些振子 Q-Q 态源自叶绿素(Chl)-Chl 相互作用,尽管人们对这些状态几乎一无所知。在这里,我们采用偏振相关的二维电子振动光谱来研究光捕获复合物 II 的混合振子 Q-Q 态的起源和动力学。我们表明,该区域的状态主要源自 Chl b,并证明了如何区分振子 Q 与 Q 特征的程度。我们发现,以 Chl b Q 为主的状态和以 Chl b Q 为主的状态的动力学明显不同,因为激发在 Q 态中持续的时间要长得多,并且 Q 动力学存在振荡成分,对此进行了讨论。我们的研究结果表明了电子-核混合在高效光捕获中的核心作用,以及 Chl a 和 Chl b 的不同功能。