The photoelectric effect is the emission of electrons from matter upon the absorption of electromagnetic radiation, such as ultraviolet radiation or x-rays. An older term for the photoelectric effect was the Hertz effect, though this phrase has fallen out of current use.*
By conservation of energy, the energy of the photon is absorbed by the electron and, if sufficient, the electron can escape from the material with a finite kinetic energy. A single photon can only eject a single electron, as the energy of one photon may only be absorbed by one electron. The electrons that are emitted are often termed photoelectrons.
The photoelectric effect helped further wave-particle duality, whereby physical systems (such as photons, in this case) display both wave-like and particle-like properties and behaviours, a concept that was used by the creators of quantum mechanics. The photoelectric effect was explained mathematically by Albert Einstein, who extended the work on quanta developed by Max Planck.
The photons of the light beam have a characteristic energy given by the wavelength of the light. In the photoemission process, if an electron absorbs the energy of one photon and has more energy than the work function, it is ejected from the material. If the photon energy is too low, however, the electron is unable to escape the surface of the material. Increasing the intensity of the light beam does not change the energy of the constituent photons, only their number, and thus the energy of the emitted electrons does not depend on the intensity of the incoming light.
Electrons can absorb energy from photons when irradiated, but they follow an "all or nothing" principle. All of the energy from one photon must be absorbed and used to liberate one electron from atomic binding, or the energy is re-emitted. If the photon is absorbed, some of the energy is used to liberate it from the atom, and the rest contributes to the electron's kinetic (moving) energy as a free particle.
In analysing the photoelectric effect quantitatively using Einstein's method, the following equivalent equations are used:
Energy of photon = Energy needed to remove an electron + Kinetic energy of the emitted electron
Algebraically:
Note: If the photon's energy (hf) is not greater than the work function (), no electron will be emitted. The work function is sometimes denoted .
In 1839, Alexandre Edmond Becquerel observed the photoelectric effect via an electrode in a conductive solution exposed to light. In 1873, Willoughby Smith found that selenium is photoconductive.
Heinrich Hertz, in 1887, made observations of the photoelectric effect and of the production and reception of electromagnetic (EM) waves, published in the journal Annalen der Physik. His receiver consisted of a coil with a spark gap, whereupon a spark would be seen upon detection of EM waves. He placed the apparatus in a darkened box in order to see the spark better; he observed, however, that the maximum spark length was reduced when in the box. A glass panel placed between the source of EM waves and the receiver absorbed ultraviolet radiation that assisted the electrons in jumping across the gap. When removed, the spark length would increase. He observed no decrease in spark length when he substituted quartz for glass, as quartz does not absorb UV radiation.
Hertz concluded his months of investigation and reported the results obtained. He did not further pursue investigation of this effect, nor did he make any attempt at explaining how the observed phenomenon was brought about.
In 1899, Joseph John Thomson investigated ultraviolet light in Crookes tubes. Influenced by the work of James Clerk Maxwell, Thomson deduced that cathode rays consisted of negatively charged particles, later called electrons, which he called "corpuscles". In the research, Thomson enclosed a metal plate (a cathode) in a vacuum tube, and exposed it to high frequency radiation. It was thought that the oscillating electromagnetic fields caused the atoms' field to resonate and, after reaching a certain amplitude, caused a subatomic "corpuscle" to be emitted, and current to be detected. The amount of this current varied with the intensity and color of the radiation. Larger radiation intensity or frequency would produce more current.
On November 5 1901, Nikola Tesla received the (Apparatus for the Utilization of Radiant Energy) that describes radiation charging and discharging conductors by "radiant energy". Tesla used this effect to charge a capacitor with energy by means of a conductive plate. The patent specified that the radiation included many different forms.
In 1902, Philipp von Lenard observed * the variation in electron energy with light frequency. He used a powerful electric arc lamp which enabled him to investigate large changes in intensity, and had sufficient power to enable him to investigate the variation of potential with light frequency. His experiment directly measured potentials, not electron kinetic energy: he found the electron energy by relating it to the maximum stopping potential (voltage) in a phototube. He found that the calculated maximum electron kinetic energy is determined by the frequency of the light. For example, an increase in frequency results in an increase in the maximum kinetic energy calculated for an electron upon liberation - ultraviolet radiation would require a higher applied stopping potential to stop current in a phototube than blue light. However Lenard's results were qualitative rather than quantitative because of the difficulty in performing the experiments: the experiments needed to be done on freshly cut metal so that the pure metal was observed, but it oxidised in a matter of minutes even in the partial vacuums he used. The current emitted by the surface was determined by the light's intensity, or brightness: doubling the intensity of the light doubled the number of electrons emitted from the surface. Lenard did not know of photons.
Albert Einstein's mathematical description in 1905 of how it was caused by absorption of what were later called photons, or quanta of light, in the interaction of light with the electrons in the substance, was contained in the paper named "On a Heuristic Viewpoint Concerning the Production and Transformation of Light". This paper proposed the simple description of "light quanta" (later called "photons") and showed how they could be used to explain such phenomena as the photoelectric effect. The simple explanation by Einstein in terms of absorption of single quanta of light explained the features of the phenomenon and helped explain the characteristic frequency. Einstein's explanation of the photoelectric effect won him the Nobel Prize of 1921.
The idea of light quanta was motivated by Max Planck's published law of black-body radiation ("On the Law of Distribution of Energy in the Normal Spectrum". Annalen der Physik 4 (1901)) by assuming that Hertzian oscillators could only exist at energies E proportional to the frequency f of the oscillator by E = hf, where h is Planck's constant. Einstein, by assuming that light actually consisted of discrete energy packets, wrote an equation for the photoelectric effect that fit experiments. This was an enormous theoretical leap and the reality of the light quanta was strongly resisted. The idea of light quanta contradicted the wave theory of light that followed naturally from James Clerk Maxwell's equations for electromagnetic behavior and, more generally, the assumption of infinite divisibility of energy in physical systems. Even after experiments showed that Einstein's equations for the photoelectric effect were accurate there was resistance to the idea of photons, since it appeared to contradict Maxwell's equations, which were believed to be well understood and well verified.
Einstein's work predicted that the energy of the ejected electrons would increase linearly with the frequency of the light. Perhaps surprisingly, that had not yet been tested. In 1905 it was known that the energy of the photoelectrons increased with increasing frequency of incident light, but the manner of the increase was not experimentally determined to be linear until 1915 when Robert Andrews Millikan showed that Einstein was correct *.
The photoelectric effect helped propel the then-emerging concept of the dual nature of light, that light exhibits characteristics of waves and particles at different times. The effect was impossible to understand in terms of the classical wave description of light, as the energy of the emitted electrons did not depend on the intensity of the incident radiation. Classical theory predicted that the electrons could 'gather up' energy over a period of time, and then be emitted. For such a classical theory to work a pre-loaded state would need to persist in matter. The idea of the pre-loaded state was discussed in Millikan's book Electrons (+ & -) and in Compton and Allison's book X-Rays in Theory and Experiment. These ideas were abandoned.
This must be done in a high vacuum environment, since the electrons would be scattered by air.
A typical electron energy analyzer is a concentric hemispherical analyser (CHA), which uses an electric field to divert electrons different amounts depending on their kinetic energies. For every element and core atomic orbital there will be a different binding energy. The many electrons created from each will then show up as spikes in the analyzer, and can be used to determine the elemental composition of the sample. Photoelectron spectroscopy
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