title: Chemiluminescence of Coelenterazine and Fluorescence of Coelenteramide: A Systematic Theoretical Study.
abstract: A systematic investigation of the structural and spectroscopic properties of coelenteramide has been performed at the TD-CAM-B3LYP/6-31+G(d,p) level of theory, including various fluorescence and chemiluminescence states. The influence of geometric conformations, solvent polarity, protonation state, and the covalent character of the O-H bond of the hydroxyphenyl moiety were carefully studied. Striking differences in geometries and electronic structures among the states responsible for light emission were characterized. All fluorescence states can be described as a limited charge transfer process for a planar amide moiety. However, the chemiluminescence state is characterized by a much larger charge transfer that takes place over a longer distance. Moreover, the chemiluminescent coelenteramide structure exhibits an amide moiety that is no longer planar, in agreement with recent, more accurate ab initio results [Roca-Sanjuán et al. J. Chem. Theory Comput.2011, 7, 4060]. Because the chemiluminescence state appears to be completely dark, a new mechanism is tentatively introduced for this process.
authors.affiliation: Key Laboratory of Theoretical and Computational Photochemistry (Beijing Normal University), Ministry of Education, College of Chemistry, Beijing Normal University , Beijing 100875, China.
authors.forename: Shu-Feng
authors.initials: SF
authors.lastname: Chen
authors.affiliation: Université Paris-Est , Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée, France.|Molecular Science Institute, School of Chemistry, University of the Witwatersrand , PO Wits Johannesburg 2050, South Africa.
authors.forename: Isabelle
authors.initials: I
authors.lastname: Navizet
authors.affiliation: Department of Chemistry-Ångström, the Theoretical Chemistry Programme, Uppsala University , P.O. Box 518, S-75120 Uppsala, Sweden.
authors.forename: Daniel
authors.initials: D
authors.lastname: Roca-Sanjuán
authors.affiliation: Department of Chemistry-Ångström, the Theoretical Chemistry Programme, Uppsala University , P.O. Box 518, S-75120 Uppsala, Sweden.
authors.forename: Roland
authors.initials: R
authors.lastname: Lindh
authors.affiliation: Key Laboratory of Theoretical and Computational Photochemistry (Beijing Normal University), Ministry of Education, College of Chemistry, Beijing Normal University , Beijing 100875, China.
authors.forename: Ya-Jun
authors.initials: YJ
authors.lastname: Liu
authors.affiliation: Aix-Marseille Université , Institut de Chimie Radicalaire, 13397 Marseille Cedex 20, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Ferré