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Principles and Applications of Fluorescence Spectroscopy

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With reference to absorption spectroscopy,we deal herewith photon absorption by electrons distributed within specific orbitals in a population of molecules. Upon absorption, one electron reaches an upper vacant orbital of higher energy. Thus, light absorption would induce the molecule excitation. Transition from ground to excited state is accompanied by a redistribution of an electronic cloud within the molecular orbitals. This condition is implicit for transitions to occur. According to the Franck–Condon principle, electronic transitions are so fast that they occur without any change in nuclei position, that is, nuclei have no time to move during electronic transition. For this reason, electronic transitions are always drawn as vertical lines.

The energy of a pair of atoms as a function of the distance separating them is given by the Morse curve. Re is the equilibrium bond distance. At this distance, the molecule is in its most stable position, and so its energy is called the molecular equilibrium energy, which is expressed as E0 or Ee. Stretching or compressing the bond induces an energy increase. On the left-hand side of Re, the two atoms become increasingly closer, inducing repulsion forces. Thus, an energy increase will be observed as a consequence of these repulsion forces. On the right-hand side of Re, the distance between the two atoms increases, and there will be attraction forces so that an equilibrium distance can be reached. Thus, an energy increase will be observed as result of the attraction forces. In principle, a harmonic oscillation should be obtained, but this is not the case. In fact, beyond a certain distance between the two atoms, the attraction forces will exert no more influence, and attraction energy will reach a plateau. Therefore, the Morse curve is anharmonic.
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