Dominik Lindorfer, Frank Müh, Robin Purchase, Elmars Krauszs, Thomas Renger,
"Non-conservative circular dichroism of photosystem II reaction centers: Is there an enhancement by a coupling with charge transfer states?"
, in Journal of Photochemistry and Photobiology A: Chemistry, Vol. 404, Seite(n) 112883, 1-2021, ISSN: 1010-6030
Original Titel:
Non-conservative circular dichroism of photosystem II reaction centers: Is there an enhancement by a coupling with charge transfer states?
Sprache des Titels:
Englisch
Original Kurzfassung:
The non-conservative nature of the circular dichroism (CD) spectrum of the Q(y) spectral region of the D1/D2/Cytb(559) reaction center complexes of photosystem II is investigated. Our theory, in addition to the usual excitonic couplings between the Q(y) transitions of the chlorophyll and pheophytin pigments, takes into account the coupling of the Q(y) with the higher-energy B-x, B-y and Nx+xy transitions of these pigments and with S-0 -> S-2 transitions of the two beta-carotene pigments close to the reaction center. The higher-energy transitions are parameterized by quantum chemical calculations and an analysis of the experimental oscillator strength of the isolated pigments. The excitonic couplings between pigments are obtained with the Poisson-TrEsp method. The coupling between exciton and charge transfer states in the central P-D1-P-D2 dimer is implicitly taken into account by a scaling factor of the excitonic coupling. The observed non-conservativity of the Q(y) CD spectrum can be qualitatively understood by the above described mixing of Q(y) and higher-energy transitions. The analysis suggests that the non-conservativity may be enhanced by coupling to charge transfer states. We expect that the present study will stimulate explicit microscopic studies of the charge transfer states in the reaction center of photosystem II.
Sprache der Kurzfassung:
Englisch
Journal:
Journal of Photochemistry and Photobiology A: Chemistry
Forschungs-