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Title: Competition between photodetachment and autodetachment of the 2{sup 1}ππ{sup *} state of the green fluorescent protein chromophore anion

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 S{sub 0}, we observe resonant excitation of the 2{sup 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.
Authors:
; ; ; ;  [1] ; ;  [2]
  1. Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)
  2. Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ (United Kingdom)
Publication Date:
OSTI Identifier:
22304345
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 20; Other Information: (c) 2014 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; ELECTRON DETACHMENT; ELECTRON EMISSION; EXCITATION; FLUORESCENCE; PHOTOELECTRON SPECTROSCOPY; PROTEINS; RADICALS