When an electron is bound to an atom, it has a potential energy that is inversely proportional to its distance from the nucleus. This is measured by the amount of energy needed to unbind the electron from the atom, and is usually given in units of electronvolts (eV). In the quantum mechanical model, a bound electron can only occupy a set of states centered on the nucleus, and each state corresponds to a specific energy level. The lowest energy state of a bound electron is called the ground state, while an electron at a higher energy level is in an excited state.
For an electron to transition between two different states, it must absorb or emit a photon at an energy matching the difference in the potential energy of those levels. The energy of an emitted photon is proportional to its frequency, so these specific energy levels appear as distinct bands in the electromagnetic spectrum.Each element has a characteristic spectrum that can depend on the nuclear charge, subshells filled by electrons, the electromagnetic interactions between the electrons and other factors.
An example of absorption lines in a spectrum.
When a continuous spectrum of energy is passed through a gas or plasma, some of the photons are absorbed by atoms, causing electrons to change their energy level. Those excited electrons that remain bound to their atom spontaneously emit this energy as a photon, traveling in a random direction, and so drop back to lower energy levels. Thus the atoms behave like a filter that forms a series of dark absorption bands in the energy output. (An observer viewing the atoms from a view that doesn't include the continuous spectrum in the background, instead sees a series of emission lines from the photons emitted by the atoms.) Spectroscopic measurements of the strength and width of spectral lines allow the composition and physical properties of a substance to be determined.
Close examination of the spectral lines reveals that some display a fine structure splitting. This occurs because of spin-orbit coupling, which is an interaction between the spin and motion of the outermost electron. When an atom is in an external magnetic field, spectral lines become split into three or more components; a phenomenon called the Zeeman effect. This is caused by the interaction of the magnetic field with the magnetic moment of the atom and its electrons. Some atoms can have multiple electron configurations with the same energy level, which thus appear as a single spectral line. The interaction of the magnetic field with the atom shifts these electron configurations to slightly different energy levels, resulting in multiple spectral lines.[97] The presence of an external electric field can cause a comparable splitting and shifting of spectral lines by modifying the electron energy levels, a phenomenon called the Stark effect.[98]
If a bound electron is in an excited state, an interacting photon with the proper energy can cause stimulated emission of a photon with a matching energy level. For this to occur, the electron must drop to a lower energy state that has an energy difference matching the energy of the interacting photon. The emitted photon and the interacting photon then move off in parallel and with matching phases. That is, the wave patterns of the two photons are synchronized. This physical property is used to make lasers, which can emit a coherent beam of light energy in a narrow frequency band.
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