Chemical and Biological Engineering ETDs

Publication Date

Summer 7-28-2026

Abstract

Photosynthetic light-harvesting complexes harvest solar energy and direct electronic excitations toward reaction centers with exceptional efficiency. This dissertation models the Fenna--Matthews--Olson complex of green sulfur bacteria, coupled to the PscA1 reaction center, as a chromophoric network. Forster resonance energy transfer theory, validated against numerically exact hierarchical equations of motion, was implemented in kinetic Monte Carlo simulations to resolve fine-grained excitation-transport pathways. The predicted charge-transfer efficiency of 77\% agrees with experiment, with the FMO2 monomer and its gateway pigment governing interfacial transfer. Systematic single, multi, and symmetry-preserving site removals, interpreted through Mobius inversion, identify critical pigments and show that cooperative effects are largely pairwise. A rigid-docking protocol adds candidate chromophores to assess whether transport can be enhanced; added pigments generally slow transfer, indicating that the native architecture is already highly optimized. These results suggest design principles for robust, efficient artificial light-harvesting systems.

Keywords

Chromophore Networks, Excitation Energy Transfer, Exciton Transport, Fenna–Matthews–Olson Complex, Förster Resonance Energy Transfer, Photosynthetic Light Harvesting

Document Type

Dissertation

Language

English

Degree Name

Chemical Engineering

Level of Degree

Doctoral

Department Name

Chemical and Biological Engineering

First Committee Member (Chair)

William P. Bricker

Second Committee Member

Dimiter N. Petsev

Third Committee Member

Oleg V. Prezhdo

Third Advisor

Andrew P. Shreve

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