Femtosecond real-time probing of the excited-state intramolecular proton transfer reaction in methyl salicylate.

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ID: 41039
2019
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Abstract
The excited-state intramolecular proton transfer (ESIPT) process and subsequent electronic relaxation dynamics in methyl salicylate have been investigated using femtosecond time-resolved ion yield spectroscopy combined with time-resolved photoelectron imaging. Excitation with a tunable pump pulse populates the keto tautomer in the first excited electronic state S(ππ). As a hydrogen atom transfers from the phenolic group to the carbonyl group within 100 fs, the molecular geometry changes gradually, leading to a variation in the electronic photoionization channel. By virtue of the accidental resonance with some intermediate Rydberg states, the time-dependent photoelectron spectra provide a direct mapping of the ESIPT reaction from the initially populated keto tautomer to the proton-transferred enol tautomer. Subsequently, the population around the enol configuration undergoes intramolecular vibrational redistribution on a subpicosecond time scale, followed by internal conversion to the ground state with a wavelength-dependent lifetime in the picosecond range. Furthermore, the excitation energies of several Rydberg states in methyl salicylate are determined experimentally.
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Authors Ling, Fengzi;Liu, Dejun;Li, Shuai;Li, Wei;Zhang, Bing;Wang, Pengfei;
Journal The Journal of Chemical Physics
Year 2019
DOI
10.1063/1.5115307
URL
Keywords Keywords not found

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