Magnetic-field-induced orientation of photosynthetic reaction centers as revealed by time-resolved W-band EPR of spin-correlated radical paris: Development of a molecular model

Spin-correlated radical pairs are the short-lived intermediates of the primary energy conversion steps of photosynthesis. In this paper, we develop a comprehensive model for the spin-polarized electron paramagnetic resonance (EPR) spectra of these systems. Particular emphasis is given to a proper treatment of the alignment of the photosynthetic bacteria by the field of the EPR spectormeter. The model is employed to analyze time-resolved W-band (94 GHz) EPR spectra of the secondary radical pair P ₇₀₀ ⁺ A ₁ ^? in photosystem I formed by photoexcitation of the deuterated and¹⁵N-substituted cyanobacteriumSynechococcus lividus. Computer simulations of the angular-dependent EPR spectra of P^700/+A_1/? provide values for the order parameter of the cyanobacterial cells and for the orientation of the membrane normal in a molecular reference system. The order parameter from EPR compares favorably with corresponding data from electron microscopy obtained for theS. lividus cells under similar experimental conditions. It is shown that high-field EPR of a magnetically aligned sample in combination with the study of quantum beat oscillations represents a powerful structural tool for the short-lived radical pair intermediates of photosynthesis.