Abstract
In previous chapters it was seen that absorption and emission of energy in the range 1 nm to 1000 nm corresponded to changes in electronic energy involving transitions between atomic or molecular electronic energy levels. Such transitions involved an initial electronic energy level and a final electronic energy level, and the electromagnetic radiation absorbed or emitted in the process was exactly equal to the difference in energy between the two energy levels. Consider the absorption process, where the electron is excited by absorption of eletromagnetic radiation from a lower to a higher energy level. If the energy of the electromagnetic radiation is greater than the difference between the initial electronic energy level and any higher energy level the electron will actually leave the atom or molecule and travel in free space with a velocity determined by the energy difference between the initial energy level and the energy of the electromagnetic radiation. The final state in this situation is not quantized and there are thus no selection rules that restrict the possible transitions, and, provided that the electromagnetic energy is large enough, all the electrons in an atom or molecule can be considered. The ejection of electrons from atoms or molecules by electromagnetic radiation in this way is known as the photoelectric effect, and the process is illustrated in Fig. 7.1.
Molecular orbital diagram for the oxygen (O2), showing a typical electronic transition (x), photoelectrons ejected from the valence orbitals using 21.21 e V radiation (c, d, e, f) and 1253.6 eV radiation [r, s, t, u = (c - f) + 1232 eV], and photoelecrtons from the core orbital using 253.6 eV radiation (v).
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Straughan, B.P., Walker, S. (1976). Photoelectron Spectroscopy. In: Straughan, B.P., Walker, S. (eds) Spectroscopy. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-5741-1_7
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DOI: https://doi.org/10.1007/978-94-009-5741-1_7
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