title: Competition between photodetachment and autodetachment of the 2(1)ππ* state of the green fluorescent protein chromophore anion.
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.
authors.affiliation: Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
authors.forename: Ciarán R S
authors.initials: CR
authors.lastname: Mooney
authors.affiliation: Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Parkes
authors.affiliation: Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
authors.forename: Lijuan
authors.initials: L
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
authors.forename: Helen C
authors.initials: HC
authors.lastname: Hailes
authors.affiliation: Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, United Kingdom.
authors.forename: Alexandra
authors.initials: A
authors.lastname: Simperler
authors.affiliation: Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, United Kingdom.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Bearpark
authors.affiliation: Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
authors.forename: Helen H
authors.initials: HH
authors.lastname: Fielding
mesh_terms: D000838:Anions / Q000737:chemistry*; D004583:Electrons; D049452:Green Fluorescent Proteins / Q000737:chemistry*; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D014732:Vibration
chemical_list: D000838:Anions; D049452:Green Fluorescent Proteins