Energy-Transfer Phenomena and Dissociation Processes in Electronically Excited Molecules

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Abstract
This paper is an extension of previous work by Magee and Funabashi on the influence of electronic coupling on dissociation mechanisms. The same model (linear chain of diatomic molecules) has again been considered. The use of a dynamical version of the Hellmann—Feynman theorem allows the development of a unified treatment valid for any coupling. An application to an infinite linear chain of hydrogen moleculeions is made, and the following results are found: (1) In the weak‐coupling case, immediate dissociation occurs. (2) In the intermediate case, the electronic excitation energy is converted into vibrational energy, mainly localized on the molecule initially excited. Redistribution of the vibrational energy then occurs. (3) In the strong‐coupling case, dissociation does not occur. Many molecules vibrate with comparable amplitudes. Short chains, containing two, three, four, and seven molecules, are also considered. For these it is found that two or more dissociations usually occur regardless of the type of coupling and initial position of the excitation. Finally, an application to intramolecular energy transfer is attempted. The case of the radiation induced isomerization of cis‐polybutadiene into its trans isomer, studied by Golub, is examined. With certain restrictions, our results can be considered as supporting Golub's views.

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