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"Dynamics of excited-state proton transfer systems via time-resolvedphotoelectron spectroscopy" S. Lochbrunner, T. Schultz, M. Schmitt, J.P. Shaffer, M.Z. Zgierski and A. StolowJ. Chem. Phys. 114 (2001), 2519-2522 Abstract: We investigate the applicability of time-resolved photoelectron spectroscopy to excited state intramolecular proton transfer (ESIPT) and internal conversion dynamics in the model system o-hydroxybenzaldehyde (OHBA) and related compounds. Photoelectron spectra of both the excited state enol and keto tautomers were obtained as a function of pump laser wavelength and pump-probe time delay. The ESIPT was found to occur in less than 50 fs over the whole absorption range of the S1(pp*) state for both OHBA and its monodeuterated analogue, suggestive of a small or non-existent barrier. The subsequent keto internal conversion rate in OHBA varies from 0.63 to 0.17 ps-1 over the S1(pp*) absorption band and the OD-deuterated analogue shows no significant isotope effect. Based upon ab initio calculations and comparison with the two-ring analogue, 1-hydroxy-2-acetonaphthone (HAN), we suggest that the internal conversion dynamics in OHBA are influenced by interactions with a close-lying np* state. BMO authors (in alphabetic order): Stefan Lochbrunner Order Hardcopy  WWW-Version |