Ab initio model for the chlorophyll-lutein exciton coupling in the LHCII complex.

2Ag- state of lutein plays a crucial role in photoprotection of higher plants. Due to its multiconfigurational nature, accurate description of this electronic state and respective transition properties is a formidable task. In this paper, applicability of various CASSCF and RASSCF formulations for description of the 2Ag- state is discussed. It is shown that inclusion of the entire π-system of lutein into the active space is required for accurate calculation of transition properties. Exciton coupling in the chlorophyll-lutein dimer involved in non-photochemical quenching in the LHCII complex was calculated to provide a connection between pigment interactions and non-photochemical quenching regulation.