Theoretical Molecular Biophysics by Philipp O.J. Scherer & Sighart F. Fischer

Author:Philipp O.J. Scherer & Sighart F. Fischer
Language: eng
Format: epub
Publisher: Springer Berlin Heidelberg, Berlin, Heidelberg

(18.57)

induces transitions to other Born–Oppenheimer states (Fig. 18.4)

(18.58)

In lowest order, the decay rate is the sum over all final states [67, 68]

(18.59)

with the matrix element

(18.60)

If the lowest order vanishes, e.g., if it is forbidden by symmetry, higher orders also have to be considered and the matrix element of the interaction has to be replaced by the corresponding element of the T-matrix [69] to obtain the generalized golden rule

(18.61)

Fig. 18.4Radiationless transitions. Transition from a higher electronic state (i) to a lower one (f). Energy conservation is possible if vibrational excitations in the final state are created. The multidimensional nuclear coordinates are represented schematically by the coordinate R

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