The f–f radiationless transitions in lanthanide complexes

A general theory of the f–f radiationless transitions in lanthanide complexes is developed within the framework of the dynamic coupling model. The two different mechanisms are discussed: the static mechanism linked with the metal bond involving vibrations as the promoting modes and the dynamic mechanism linked with the internal ligand vibrations as the promoting modes. It is found that the electronic factors for the f–f radiationless transitions may be calculated as a sum of three products of the unit tensor operators Uλ and the parameters ηλ independent of the nature of the electronic states involved in the transition. An approximate expression for the rate constant is derived and possible application to the quantitative analysis of the f–f radiationless transitions is discussed.

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