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

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Abstract
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 activation energy (43.4 kJ/mol−1) for this photoejection mechanism. A Markov random walk matrix method is adopted in order to analyze the photoelectron process in different mixture configurations. Good agreement between observed and theoretical results over the entire solvent concentration range for both the fluorescence decay rates and the fluorescence quantum yields at various temperatures between −15 and +75 °C supports the assumed model. It is interesting to speculate about possible roles of threshold electrons in chemical and biological long range electron transfer reactions.