Issue 10, 2013

Understanding photosynthetic light-harvesting: a bottom up theoretical approach


We discuss a bottom up approach for modeling photosynthetic light-harvesting. Methods are reviewed for a full structure-based parameterization of the Hamiltonian of pigment–protein complexes (PPCs). These parameters comprise (i) the local transition energies of the pigments in their binding sites in the protein, the site energies; (ii) the couplings between optical transitions of the pigments, the excitonic couplings; and (iii) the spectral density characterizing the dynamic modulation of pigment transition energies and excitonic couplings by protein vibrations. Starting with quantum mechanics perturbation theory, we provide a microscopic foundation for the standard PPC Hamiltonian and relate the expressions obtained for its matrix elements to quantities that can be calculated with classical molecular mechanics/electrostatics approaches including the whole PPC in atomic detail and using charge and transition densities obtained with quantum chemical calculations on the isolated building blocks of the PPC. In the second part of this perspective, the Hamiltonian is utilized to describe the quantum dynamics of excitons. Situations are discussed that differ in the relative strength of excitonic and exciton-vibrational coupling. The predictive power of the approaches is demonstrated in application to different PPCs, and challenges for future work are outlined.

Graphical abstract: Understanding photosynthetic light-harvesting: a bottom up theoretical approach

Article information

Article type
28 Sep 2012
11 Jan 2013
First published
14 Jan 2013
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2013,15, 3348-3371

Understanding photosynthetic light-harvesting: a bottom up theoretical approach

T. Renger and F. Müh, Phys. Chem. Chem. Phys., 2013, 15, 3348 DOI: 10.1039/C3CP43439G

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