When photon energies are as high as the electron rest energy of , yet another process, Compton scattering, may occur. Above twice this energy, at , pair production is also more likely. Compton scattering and pair production are examples of two other competing mechanisms.
Even if the photoelectric effect is the favoured reaction for a particular interaction of a single photon with a bound electron, the result is also subject to quantum statistics and is not guaranteed. The probability of the photoelectric effect occurring is measured by the cross section of the interaction, σ. This has been found to be a function of the atomic number of the target atom and photon energy. In a crude approximation, for photon energies above the highest atomic binding energy, the cross section is given by:
Here Z is the atomic number and n is a number which varies between 4 and 5. The photoelectric effect rapidly decreases in significance in the gamma-ray region of the spectrum, with increasing photon energy. It is also more likely from elements with high atomic number. Consequently, high-Z materials make good gamma-ray shields, which is the principal reason why lead (Z = 82) is preferred and most widely used.