Existence of a Light Intensity Threshold for Photoconversion Processes

Two models of the mechanism of photoinduced electron transfer at semiconductor surfaces have long been differentiated by their prediction, or their denial, of the existence of a light intensity threshold for fuel-forming photoconversion processes. We attempt to clarify this problem by making a distinction between two possible types of thresholds: a threshold for incipient product formation and a threshold for product formation in a specified state, such as its standard state. A light intensity threshold for incipient product formation appears to be forbidden by molecular electron-transfer theory and has apparently never been observed. Conversely, a light intensity threshold for product formation in its standard state must always occur, simply because the product concentration must first build up from its equilibrium value to its standard-state value. Since the former threshold is forbidden, while the latter is unavoidable, the existence of a threshold cannot be used to distinguish between the models.