We have examined the photophysics of energy migration and trapping in photosystem I by investigating the spectral and temporal properties of the fluorescence from the core antenna chlorophylls as a function of the antenna size. Time-correlated single photon counting was used to determine the fluorescence lifetimes in the isolated P700 chlorophyll a-protein complex and in a mutant of Chlamydomonas reinhardtii that lacks the photosystem II reaction center complex. The fluorescence decay in both types of sample is dominated by a fast (1545 psec) component that is attributed to the lifetime of excitations in the photosystem I core antenna. These excitations decay primarily by an efficient photochemical quenching on P700. The measured lifetimes show a linear relationship to the core antenna size. A linear dependence of the excitation lifetime on antenna size was predicted previously in a lattice model for excitation migration and trapping in arrays of photosynthetic pigments [Pearlstein, R. M. (1982) Photochem. Photobiol. 35, 83544M]. Based on this model, our data predict a time constant for photochemical charge separation in the photosystem I reaction center of 2.8 ± 0.7 or 3.4 ± 0.7 psec, assuming monomeric or dimeric P700, respectively. The predicted average single-step transfer time for excitation transfer between core antenna pigments is 0.21 ± 0.04 psec. Under these conditions, excitation migration in photosystem I is near the diffusion limit, with each excitation making an average of 2.4 visits to the reaction center before photoconversion.The primary steps in photosynthesis are absorption of light and creation of a singlet excitation, transfer of the excitation between pigment molecules, and photochemical charge separation in the reaction center. The relative kinetics of the excitation transfer and trapping reactions determine critical aspects of the overall light-harvesting process. Excitation transfer is believed to occur by an incoherent hopping mechanism (1), with the excitation following a random walk through the antenna pigments to the reaction center (2). The mechanism of charge separation depends on the unique redox properties of the reaction center pigments in the excited state and appears to be similar in bacteria and plants.The reaction center complex of purple photosynthetic bacteria contains only six pigment molecules (3), at least four of which are directly involved in the primary photochemical reactions (4). This relative simplicity has permitted measurement of the photochemical rate constant, kp, by direct excitation of the reaction center pigments (5-7). In contrast, the photosystem I and II (PSI and PSII) reaction center complexes isolated from oxygen-evolving plants contain a relatively large number (40-110) of chlorophyll a (Chl-a) molecules (8, 9). The presence of these core antenna pigments in reaction center preparations complicates spectroscopic and kinetic measurements of the primary photochemical reactions because of substantial overlap between the absorptions ofthe reaction...