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Charge separation in 9,9′‐dianthryl and a special pair treated by a semi‐empirical reaction field method
Author(s) -
Larsson S.,
Källbring B.
Publication year - 1990
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560381719
Subject(s) - chromophore , photosynthetic reaction centre , charge (physics) , dipole , chemistry , bent molecular geometry , field (mathematics) , interpolation (computer graphics) , partial charge , solvent polarity , molecular physics , polarity (international relations) , computational chemistry , photochemistry , chemical physics , solvent , physics , quantum mechanics , mathematics , classical mechanics , electron transfer , organic chemistry , motion (physics) , biochemistry , pure mathematics , cell
Abstract Reaction fields are introduced to treat charge transfer excitations in chromophore systems. The methods are tested on the 9,9′‐dianthryl dimeric molecule. The energy shift of the low energy component in dual fluorescence is a function of the polarity of the solvent and is correctly reproduced if an interpolation formula is used between the Mataga‐Nishimoto and Ohno–Klopman approximations for the bi‐centric γ integrals. The model is then applied to the special pair of the photosynthetic reaction center of Rhodopseudomonas viridis . This special pair is found to have an S 1 state with dipolar character, corresponding to partial M ← L charge transfer. The bias is due to the bent shape of the M chromophore.

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