Franck-Condon factor sum rules for transitions involving bound and unbound states

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Electron Transitions, Franck-Condon Principle, Molecular Energy Levels, Oscillator Strengths, Transition Probabilities, Formalism, Photodissociation, Rotational Spectra

Scientific paper

The sum rule formalism for Franck-Condon factors and related quantities is considered for the following molecular transitions: (1) bound-bound, (2) bound-bound + free, (3) free-bound + free, and (4) free-free. The bound states are normally vibrational levels in electronic potential wells. The unbound states include the continuum above the dissociation limit of bound molecular potentials and also of completely unbound repulsive potentials. The sum rules for each of the transitions are compared and discussed in the context of the distribution of oscillator strengths across molecular band systems.

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