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Direct and Superexchange Couplings for Electron Transfer in Donor-Bridge-Acceptor Systems
Hangjing Zheng1, Xinyuan Feng1, Wei Wu1
1State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, China.
None:
This work investigates the direct and superexchange couplings in donor-bridge-acceptor electron transfer molecules by extracting diabatic information from the adiabatic wave functions obtained from multiconfigurational self-consistent field methods. Based on the numerical values of these couplings, the electron transfer mechanisms are derived for the three model systems, including 1,4-diazabicyclo[2.2.2]octane radical cation, [3,3]-spirarene, and [Fe(H2O)6-H2O-Fe(H2O)6]5+, namely that spirarene and the other two molecules are controlled by the direct and superexchange mechanisms, respectively.
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