Indole: A model system for one‐photon threshold photoionization in polar media

Indole in a sufficiently polar medium, such as water, presents a relatively simple example of the one‐photon near‐threshold photoionization process in the condensed phase. This photoejection mechanism is the main object of study in this paper. To carry out this study, dynamic processes of indole in its first excited singlet state S1 are explored as a function of temperature in mixed water/methanol solvents. In mixed solvents having high water content, the dominant radiationless transition in the higher temperature regimes is a localized photoejection process. In pure methanol, electron photoejection is unimportant, indicating a distinction between aqueous solvents and other hydrophilic solvents that goes far beyond dielectric constant considerations. A water ‘‘cage,’’ composed of 4±1 water molecules, and probably quite close to the parent cation, is the electron acceptor. The apparently unique structure of this water cluster, different from that in normal water, is thought to be responsible for the large ...

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