title: Absorption and emission of the apigenin and luteolin flavonoids: a TDDFT investigation.
abstract: The absorption and emission properties of the two components of the yellow color extracted from weld (Reseda luteola L.), apigenin and luteolin, have been extensively investigated by means of DFT and TDDFT calculations. Our calculations reproduce the absorption spectra of both flavonoids in good agreement with the experimental data and allow us to assign the transitions giving rise to the main spectral features. For apigenin, we have also computed the electronic spectrum of the monodeprotonated species, providing a rationale for the red-shift of the experimental spectrum with increasing pH. The fluorescence emission of both apigenin and luteolin has then been investigated. Excited-state TDDFT geometry optimizations have highlighted an excited-state intramolecular proton transfer (ESIPT) from the 5-hydroxyl to the 4-carbonyl oxygen of the substituted benzopyrone moiety. By computing the potential energy curves at the ground and excited states as a function of an approximate proton transfer coordinate for apigenin, we have been able to trace an ESIPT pathway and thus explain the double emission observed experimentally.
authors.affiliation: Dipartimento di Chimica, Università degli Studi di Perugia, via Elce di Sotto 8, I-06123 Perugia, Italy.
authors.forename: Anna
authors.initials: A
authors.lastname: Amat
authors.forename: Catia
authors.initials: C
authors.lastname: Clementi
authors.forename: Filippo
authors.initials: F
authors.lastname: De Angelis
authors.forename: Antonio
authors.initials: A
authors.lastname: Sgamellotti
authors.forename: Simona
authors.initials: S
authors.lastname: Fantacci
mesh_terms: D000042:Absorption; D047310:Apigenin / Q000737:chemistry*; D004583:Electrons; D047311:Luteolin / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011522:Protons; D011789:Quantum Theory; D013997:Time Factors
chemical_list: D011522:Protons; D047310:Apigenin; D047311:Luteolin