Singlet and Triplet States

Photoluminescence is divided into two categories: fluorescence and phosphorescence. A pair of electrons occupying the same electronic ground state have opposite spins and are said to be in a singlet spin state; see (a) in the illustration below.

Figure10.47

When an analyte absorbs an ultraviolet or visible photon, one of its valence electrons moves from the ground state to an excited state with a conservation of the electron’s spin (b). Emission of a photon from this singlet excited state to the singlet ground state—or between any two energy levels with the same spin—is called fluorescence. The probability of fluorescence is very high and the average lifetime of an electron in the excited state is only 10–5–10–8 s. Fluorescence, therefore, decays rapidly once the source of excitation is removed.

In some cases an electron in a singlet excited state is transformed to a triplet excited state (c) in which its spin is no longer paired with the ground state. Emission between a triplet excited state and a singlet ground state—or between any two energy levels that differ in their respective spin states–is called phosphorescence. Because the average lifetime for phosphorescence ranges from 10–4–104 s, phosphorescence may continue for some time after removing the excitation source.

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