Effects of nuclear spin polarization on reaction dynamics in photosynthetic bacterial reaction centers.
Singlet-triplet mixing in the initial radical-pair state, P[unk]I[unk], of photosynthetic bacterial reaction centers is due to the hyperfine mechanism at low magnetic fields and both the hyperfine and Deltag mechanisms at high magnetic fields (>1 kG). Since the hyperfine field felt by the electron spins in P[unk]I[unk] is dependent upon the nuclear spin state in each radical, the relative probabilities of charge recombination to the triplet state of the primary electron donor, (3)PI, or the ground state, PI, will depend on the nuclear spin configuration. As a result these recombination products will have non-equilibrium distributions of nuclear spin states (nuclear spin polarization). This polarization will persist until the (3)PI state decays. In addition, due to unequal nuclear spin relaxation rates in the diamagnetic PI and paramagnetic (3)PI states, net polarization of the nuclear spins can result, especially in experiments that involve recycling of the system through the radical-pair state. This net polarization can persist for very long times, especially at low temperatures. Nuclear spin polarization can have consequences on any subsequent process that involves re-formation of the radical-pair state.Numerical calculations of the nuclear polarization caused by both of these mechanics are presented, including the effect of such polarization on subsequent yields of (3)PI, (3)PI decay rates, the decay rate of the radical pair, and saturation behavior. The effect of this polarization under certain circumstances can be very dramatic and can explain previously noted discrepancies between experiments and theories that do not include nuclear spin polarization effects. Our analysis suggests new classes of experiments and indicates the need to reinterpret some past experimental results.
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Goldstein
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Boxer