Terrance P. Smith

Vibrational Modes and the Dynamic Solvent Effect in Electron and Proton Transfer

This article primarily reviews recent work on ultrafast experiments on excited state intramolecular electron and proton transfer, with an emphasis on experiments on chemical systems that have been analyzed theoretically. In particular, those systems that have been quantitatively characterized by static spectroscopy, which provides detailed information about the reaction potential energy surface and about other parameters that are necessary to make a direct comparison to theoretical predictions, are described.

Ultrafast studies on proton transfer in photostabilizers

Abstract Excited-state intramolecular proton transfer (ESIPT) is currently of considerable experimental theoretical interest and practical industrial interest, e.g. in polymer stabilizers. The vast majority of ESIPT systems involve transfer of a proton from an oxygen donor. 1,5-dihydroxyanthraquinone is typical, with ESIPT leading to dual fluorescence emission. The emission is conveniently discussed in terms of a four-state diagram, where N, N*, T and T* correspond to the normal 9,10-keto ground state, the normal 9,10-keto excited state, the 1,9-keto ground tautomeric state and the 1,9-keto excited tautomeric state respectively. The short-wavelength emission has been assigned to the normal excited state and the long-wavelength emission to the excited tautomer. ESIPT with nitrogen as the proton donor is rare and is often complicated by dimerization. Previous studies of 1-aminoanthraquinone and 1-(acetylamino)anthraquinone have found no evidence for ESIPT. We now report compelling evidence for ESIPT in 1-(acylamino)anthraquinones.