Towards first-principles calculation of electronic excitations in the ring of the protein-bound bacteriochlorophylls

• Published in: Chemical physics Vol. 505; pp. 34 - 39
• Main Authors: Polyakov, Igor V., Khrenova, Maria G., Moskovsky, Alexander A., Shabanov, Boris M., Nemukhin, Alexander V.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 13.04.2018
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2018.03.009

[Display omitted] •Ring of 32 BChl molecules in the LH1 bacterial antenna complex was considered.•Excitonic Hamiltonian matrix elements were estimated by quantum chemistry methods.•Excitation energy corresponding to the Qy absorption band was approximated.•Fragment approaches were utilized to evaluate contributions to excitation energy. Modeling electronic excitation of bacteriochlorophyll (BChl) molecules in light-harvesting (LH) antennae from photosynthetic centers presents a challenge for the quantum theory. We report on a quantum chemical study of the ring of 32 BChl molecules from the bacterial core complex LH1-RC. Diagonal and off-diagonal elements of the excitonic Hamiltonian matrices are estimated in quantum chemical calculations of relevant fragments using the TD-DFT and CIS approaches. The deviation of the computed excitation energy of this BChl system from the experimental data related to the Qy band maximum of this LH1-RC complex is about 0.2 eV. We demonstrate that corrections due to improvement in modeling of an individual BChl molecule and due to contributions from the protein environment are in the range of the obtained discrepancy between theory and experiment. Differences between results of the excitonic model and direct quantum chemical calculations of BChl aggregates fall in the same range.