title: Vibronic coupling in the ground and excited states of oligoacene cations.
abstract: The vibrational coupling in the ground and excited states of positively charged naphthalene, anthracene, tetracene, and pentacene molecules is studied on the basis of a joint experimental and theoretical study of ionization spectra using high-resolution gas-phase photoelectron spectroscopy and first-principles correlated quantum-mechanical calculations. Our theoretical and experimental results reveal that, while the main contribution to relaxation energy in the ground state of oligoacene systems comes from high-energy vibrations, the excited-state relaxation energies show a significant redistribution toward lower-frequency vibrations. A direct correlation is found between the nature of the vibronic interaction and the pattern of the electronic state structure.
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
authors.forename: Roel S
authors.initials: RS
authors.lastname: Sanchez-Carrera
authors.forename: Veaceslav
authors.initials: V
authors.lastname: Coropceanu
authors.forename: Demetrio A
authors.initials: DA
authors.lastname: da Silva Filho
authors.forename: Rainer
authors.initials: R
authors.lastname: Friedlein
authors.forename: Wojciech
authors.initials: W
authors.lastname: Osikowicz
authors.forename: Richard
authors.initials: R
authors.lastname: Murdey
authors.forename: Christian
authors.initials: C
authors.lastname: Suess
authors.forename: William R
authors.initials: WR
authors.lastname: Salaneck
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Brédas
mesh_terms: D000873:Anthracenes / Q000737:chemistry; D004583:Electrons; D009279:Naphthacenes / Q000737:chemistry; D009281:Naphthalenes / Q000737:chemistry; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D013057:Spectrum Analysis; D014732:Vibration
chemical_list: D000873:Anthracenes; D009279:Naphthacenes; D009281:Naphthalenes; D011084:Polycyclic Aromatic Hydrocarbons; C031721:naphthalene; C034020:anthracene; C487736:naphthacene