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Communication: Autodetachment versus internal conversion from the S1
state of the isolated GFP chromophore anion
12. L. H. Andersen, H. Bluhme, S. Boye, T. J. D. Jorgensen, H. Krogh, I. B. Nielsen, S. B. Nielsen, and A. Svendsen, Phys. Chem. Chem. Phys. 6, 2617 (2004).
15. K. B. Bravaya and A. I. Krylov, “On the photodetachment from the green fluorescent protein chromophore,” J. Phys. Chem. A (published online).
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40.The intergration ranges defining [S1] for excitation at 2.38 and 2.57 eV were 0.15 < eKE < 1.40 eV and 0.15 < eKE < 1.60 eV, respectively, reflecting that fact that the maximum of the pump-probe feature shifts to higher eKE. The integration range for that of the vibrational autodetachment stays roughly unchanged at the different photon energies used.
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The anionic form of p-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI) has been extensively employed as a model of the chromophore of the green fluorescence protein. The bright S1 excited state HBDI− has a measured lifetime of 1.4 ps in the gas-phase and is dominated by two non-radiative decay mechanisms: internal conversion and autodetachment into the neutral continuum. Here, time-resolved photoelectron spectroscopy has been used to determine the yields of these two channels from which the lifetime for autodetachment was found to be ∼30 ps.
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