Abstract
We present a general framework for analyzing how molecular structure and dynamics control the effective tunneling coupling in electron transfer reactions. Using combined molecular dynamics and electronic structure calculations, we explore four principal issues that could not be quantitatively addressed at the Pathways level: sensitivity to the choice of the electronic Hamiltonian, interference among pathways, sensitivity to the electron transfer bridge conformation and modulation by the dynamical motion of the bridge. To be able to categorize the electronic orbital interactions, to identify the most relevant ones and to investigate their sensitivity to the bridge structure and dynamics, we introduce the dynamic overlap-coupling (S – H) maps. Using this framework, we identify dominant pathways mediated by these interactions and analyze the effects of the interference among them on the effective coupling. This approach provides a clear view of how the bridge structure and dynamics controls the effective coupling, allowing for a more quantitative understanding of biological ET reactions, guiding detailed calculations and de novo design of ET proteins.
Published Version
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