Understand Phosphorescence

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In summary, the conversation discusses the topic of phosphorescence and the role of spin-orbit coupling in the first transition from a singlet state to a triplet state. The person expresses confusion about whether this coupling also exists between the ground state and the triplet state. The other person explains that in order for phosphorescence to occur, there needs to be both spin-orbit coupling and vibronic coupling between the singlet and triplet states, and also coupling to the radiation field for the transition back to the ground state. They also mention Kasha's rule, which states that vibronic coupling is not as efficient due to the large energy gap.
  • #1
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hi

i have still some troubles to understand phosphorescence:

http://en.wikipedia.org/wiki/Phosphorescence" [Broken]

wikipedia has a diagram, where an electron in an exicted state that is a singulet state falls on a second level that is a triplet state.

my problem is, that this first transition is explained by spin-orbit coupling. but is it no so, that the ground state and this triplet state should have spin-orbit coupling either?- but in this case, the transition from the triplet state to the ground state should also be possible.

so it is possible to have this coupling just between some states?

sorry about my english.
 
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  • #2


does nobody have an idea or is there anything wrong with my question?
 
  • #3


Of course there is also spin orbit (SO) coupling between S0 and T0, if not you would not observe phosphorescence.
The point is rather that for the transition from S1 to T0 you need both SO coupling and vibronic coupling while for the transition from T0 to S0 you need both SO coupling and coupling to the radiation field.
As in the case of fluorescence, the vibronic coupling between S0 and T0 is rather inefficient due to the large energy gap (Kasha's rule: http://en.wikipedia.org/wiki/Kasha's_rule )
 

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