Insights into colour-tuning of chlorophyll optical response in green plantsElectronic supplementary information (ESI) available: Additional spectra of LHC-II chromophores, decomposition of LHC-II spectra into regional contributions, images of complex chlorophyll geometries and inter-chromophore distances. See DOI: 10.1039/c5cp03392f

First-principles calculations within the framework of real-space time-dependent density functional theory have been performed for the complete chlorophyll (Chl) network of the light-harvesting complex from green plants, LHC-II. A local-dipole analysis method developed for this work has made possible the studies of the optical response of individual Chl molecules subjected to the influence of the remainder of the chromophore network. The spectra calculated using our real-space TDDFT method agree with previous suggestions that weak interaction with the protein microenvironment should produce only minor changes in the absorption spectrum of Chl chromophores in LHC-II. In addition, relative shifting of Chl absorption energies leads the stromal and lumenal sides of LHC-II to absorb in slightly different parts of the visible spectrum providing greater coverage of the available light frequencies. The site-specific alterations in Chl excitation energies support the existence of intrinsic energy transfer pathways within the LHC-II complex. First-principles calculations show that chlorophyll absorption spectra are different when located on the stromal and lumenal sides of the thylakoid membrane in the major light-harvesting complex from green plants.