According to the Grotthus – Draper Law of photo-chemistry, also called the principal of photo chemical activation,
Only that light which is absorbed by a system can bring about a photochemical change. However it is not essential that the light which is absorbed must bring about a photochemical change. The absorption of light may result in a number of other phenomena as well. For instance, the light absorbed may cause only a decrease in the intensity of the incident radiation. This event is governed by the Beer-Lambert Law. Secondly, the light absorbed may be re-emitted almost instantaneously (within second) in one or more steps. This phenomenon is known as fluorescence. The emission in fluorescence bearer with the removal of the source of light. Sometimes the light absorbed is given out slowly and even long after the removal of the source of light. This phenomenon is known as phosphorescence.
The phenomena of fluorescence and phosphorescence are best explained with the help of the Jablonski Diagram.
In order to understand this diagram, we need to define some terminology. Most molecules have an even number of electrons and thus in the ground state, all the electrons are spin paired. The quantity , where is the total electron spin, is known as the spin multiplicity of a state. When the spins are paired as shown in the figure, the upward orientation of the electron spin is cancelled by the downward orientation so that .
; so that .
Thus, the spin multiplicity of the molecule is 1. We express it by saying that the molecule is in the singlet ground state.
When by the absorption of a photon of a suitable energy , one of the paired electrons goes to a higher energy level (excited state), the spin orientations of the single electrons may be either parallel or antiparallel. [see image]
•If spins are parallel, or i.e., the spin multiplicity is 3. This is expressed by saying that the molecule is in the triplet excited state.
• If the spins are anti-parallel, then
so that i.e., the singlet excited state, as already mentioned.
Since the electron can jump to any of the higher electronic states depending upon the energy of the photon absorbed, we get a series of singlet excited states, where and a series of triplet excited state where . Thus etc are respectively known as first singlet excited state, second singlet excited state and so on. Similarly, in are respectively known as first triplet excited state, second triplet excited state and so on.
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