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The photoelectric effect is caused by the absorption of electromagnetic radiation and consists of electron ejection from a solid (or liquid) surface, usually of a metal, though nonmetals have also been studied. In the case of a gas, the term photoionization is more common, though there is basically little difference between these processes. In spite of experimental difficulties connected with surface-adsorbed gas and energy loss of ejected electrons in penetrating a layer of the solid into vacuum, early experimenters established two important features about the photoelectric effect. These are: (1) although the photoelectric current (i.e., the number of photoelectrons) is proportional to the incident-light intensity, the energy of the individual photoelectrons is independent of light intensity; and (2) the maximum energy of the ejected electron is roughly proportional to the frequency of light. These observations cannot be explained in terms of wave theory. Einstein argued that the light is absorbed in quanta of energy equal to Planck’s constant (h) times light frequency, hν, by electrons, one at a time. A minimum energy symbolized by the Greek letter psi, ψ, called the photoelectric work function of the surface, must be supplied before the electron can be ejected. When a quantum of energy is greater than the work function, photoelectric emission is possible with the maximum energy symbolized by the Greek letter epsilon, ε, of the photoelectron (εmax) being stated by Einstein’s photoelectric equation as equaling the difference between the photon energy and the work function; i.e., εmax = hν - ψ. Einstein’s interpretation gave strong support for the quantum theory of radiation. Early experiments determined Planck’s constant, h, independently through the above equation and also established the fact that an immeasurably small time delay is involved between absorption of a quantum of light and the ejection of an electron. The latter is clearly indicative of particle-like interaction.

Accurate and reliable values of the work function and ejection energy are now available for most solids; the chief obstacles to the development of such data were the difficulty of preparing clean surfaces and the energy loss of electrons in penetration into vacuum. The photoelectric threshold frequency, symbolized by the Greek letter nu with subscript zero, ν0, is that frequency at which the effect is barely possible; it is given by the ratio of the work function symbolized by the Greek letter psi, ψ, to Planck’s constant (ν0 = ψ/h). The photoelectric yield, defined as the ratio of the number of photoelectrons to that of incident photons, serves as a measure of the efficiency of the process. Photoelectric yield starts from a zero value at threshold, reaches a maximum value (about 1/1,000) at about twice the threshold frequency, and falls again when frequency is further increased. Some unusual alloys exhibit yields up to 100 times greater than normal (i.e., about 0.1). Normally the yield depends also on polarization and angle of incidence of the radiation. Parallel polarization (polarization in the plane of incidence) gives higher yield than does perpendicular polarization, in some instances by almost 10 times.