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Electronic Polarization Effect of the Water Environment in Charge-Separated Donor–Acceptor Systems: An Effective Fragment Potential Model Study
journal contribution
posted on 2016-11-30, 00:00 authored by Kazuma Yanai, Kazuya Ishimura, Akira Nakayama, Michael W. Schmidt, Mark S. Gordon, Jun-ya HasegawaThe
electronic polarization (POL) of the surrounding environment
plays a crucial role in the energetics of charge-separated systems.
Here, the mechanism of POL in charge-separated systems is studied
using a combined quantum mechanical and effective fragment potential
(QM/EFP) method. In particular, the POL effect caused by charge separation
(CS) is investigated at the atomic level by decomposition into the
POL at each polarizability point. The relevance of the electric field
generated by the CS is analyzed in detail. The model systems investigated
are Na+–Cl– and guanine–thymine
solvated in water. The dominant part of the POL arises from solvent
molecules close to the donor (D) and acceptor (A) units. At short
D–A distances, the electric field shows both positive and negative
interferences. The former case enhances the POL energy. At longer
distances, the interference is weakened, and the local electric field
determines the POL energy.