A theoretical study of the interaction between inter-molecular proton transfer and internal rotation

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This research project investigated theoretically the interaction between the inter-molecular proton transfer and the internal rotation. For this problem, an experimental research had already reported the existence of a peculiar interaction where the proton transfer reaction was enhanced by the excitation of the internal rotation. However, the detailed mechanism of this interaction has been completely unknown.In this project, new method and computer code to treat this problem were developed and were applied to the 5-methyl-9-hyodroxyphenalenone, 2-methyl-malonaldehyde and 5-methyl-tolopolone. The developed method and computer were essentially an extension of the Reaction Surface Hamiltonian method for the systems that have plural numbers of large amplitude motions. In the application, the interaction mentioned above was surely reconfirmed and the detailed mechanism of this interaction was also successfully analyzed. In addition to this analysis, a new fact was found when the internal rotation was in the highly excited states. It is that the proton transfer reaction was obstructed by the excitation of the internal rotation in the highly excited rotational states. In this project, the reason and the mechanism of this phenomenon were also analyzed.