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  • Title: Competition between photodetachment and autodetachment of the 2(1)ππ* state of the green fluorescent protein chromophore anion.
    Author: Mooney CR, Parkes MA, Zhang L, Hailes HC, Simperler A, Bearpark MJ, Fielding HH.
    Journal: J Chem Phys; 2014 May 28; 140(20):205103. PubMed ID: 24880334.
    Abstract:
    Using a combination of photoelectron spectroscopy measurements and quantum chemistry calculations, we have identified competing electron emission processes that contribute to the 350-315 nm photoelectron spectra of the deprotonated green fluorescent protein chromophore anion, p-hydroxybenzylidene-2,3-dimethylimidazolinone. As well as direct electron detachment from S0, we observe resonant excitation of the 2(1)ππ* state of the anion followed by autodetachment. The experimental photoelectron spectra are found to be significantly broader than photoelectron spectrum calculated using the Franck-Condon method and we attribute this to rapid (∼10 fs) vibrational decoherence, or intramolecular vibrational energy redistribution, within the neutral radical.
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