The role of mixed vibronic Q(y)-Q(x) states in green light absorption of light-harvesting complex II

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(y)-Q(x) 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(y)-Q(x) 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(y) versus Q(x) character. We find that the dynamics for states of predominately Chl b Q(y) versus Chl b Q(x) character are markedly different, as excitation persists for significantly longer in the Q(x) states and there is an oscillatory component to the Q(x) 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.