Electron transport through photosystem II (PSII), measured as oxygen evolution, was investigated in isolated PSII particles and thylakoid membranes irradiated with white light of intensities (I) of 20 to about 4000 mu mol of photons/(m(2)center dot s). In steady-state conditions, the evolution of oxygen varies with I according to the hyperbolic expression OEth = OEth(max)I/(L-1/2 + I) (eq i) where OEth is the theoretical oxygen evolution, OEth(max) is the maximum oxygen evolution, and L-1/2 is the light intensity giving OEth(max)/2. In this work, the mathematical derivation of this relationship was performed by using the Langmuir adsorption isotherm and assuming that the photon interaction with the chlorophyll (Chl) in the PSII reaction center is a heterogeneous reaction in which the light is represented as a stream of particles instead of an electromagnetic wave (see discussion in Turro, N. J. Modern Molecular Photochemistry; University Science Books: Mill Valley, CA, 1991). In accordance with this approximation, the Chl molecules (P680) were taken as the adsorption surfaces (or heterogeneous catalysts), and the incident (or exciting) photons as the substrate, or the reagent. Using these notions, we demonstrated that eq i (Langmuir equation) is a reliable interpretation of the photon-P680 interaction and the subsequent electron transfer from the excited state P680, i.e., P680(*), to the oxidized pheophytin (Phe), then from Phe(-) to the primary quinone Q(A). First, eq i contains specific functional and structural information that is apparent in the definition of OEth(max) as a measure of the maximal number of PSII reaction centers open for photochemistry, and L-1/2 as the equilibrium between the electron transfer from Phe(-) to Q(A) and the formation of reduced Phe in the PSII reaction center by electrons in provenance from P680(*). Second, a physiological control mechanism in eq i is proved by the observation that the magnitudes of OEth(max) and L-1/2 are affected differently by exogenous PSII stimulators of oxygen evolution (Fragata, M.; Dudekula, S. J. Phys. Chem. B 2005, 109, 14707). Finally, an unexpected new concept, implicit in eq i, is the consideration of the photon as the substrate in the photochemical reactions taking place in the PSII reaction center. We conclude that the Langmuir equation (eq i) is a novel mathematical formulation of energy and electron transfer in photosystem II.