Is the Breakdown of the Born-Oppenheimer Approximation Responsible for Internal Conversion in Large Molecules?*

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Vibronic radiationless transitions in large polyatomic molecules can be thought of as a process whereby the molecule, initially prepared in a discrete quasistationary state, makes a transition to an adjoining vibronic continuum belonging to a lower electronic state of the same multiplicity. In many instances the transition is analogous to penetration through a barrier between two „nested” potential sheets far away from an actual intersection of the sheets. Simultaneous distortions of vibrational and electronic parts of the wavefunction are required for such a tunneling process. The vibrational distortion manifests itself in the familiar Franck-Condon effect. The electronic distortion can be caused by nontotally symmetric vibrations of the molecule either because of the displaced nuclear configuration, to which the electrons instantly respond (Herzberg-Teller effect), or because of the protracted response of the electrons to the kinetic energy of nuclear motion (nonadiabatic effect or the breakdown of the Born-Oppenheimer approximation). It is found here that Herzberg-Teller coupling is more effective in causing radiationless transitions than the breakdown of the Born-Oppenheimer approximation when the potential surfaces involved are not close to an intersection.

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