Bethe-Salpeter equation insights into the photo-absorption function and exciton structure of chlorophyll a and b in light-harvesting complex II

The photo-absorption process and the excitation of chlorophyll (Chl) is the primary and essential step of photosynthesis in green plants. By solving the Bethe-Salpeter equation (BSE) on top of the GW approximation within ab initio many-body perturbation theory, we calculate the photo-absorption function and the excitons structure of Chl a and b in their in vivo conformations as measured by X-ray diffraction in the light-harvesting complex (LHC) II. BSE optical absorption spectra are in good agreement with the experiment and we discuss residual discrepancies. The experimental evidence of multiple Chla forms in vivo is explained by BSE. The Chla and Chlb BSE exciton wavefunctions present important charge-transfer differences on the Soret band. Q excitons are almost identical, apart from charge (both electron and hole) localization on the Chlb C7 aldheide formyl group, absent on the Chla methyl C7, that is exactly the group where the two chlorophylls differ.

Automated summary

The study investigates the photo-absorption and exciton structures of Chl a and b in their in vivo conformations using the Bethe-Salpeter equation. The BSE optical absorption spectra are in good agreement with the experiment, and the BSE explains the experimental evidence of multiple Chla forms.