Vibronic coupling in the ground and excited states of oligoacene cations.
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.
Sanchez-Carrera
Roel S
RS
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Coropceanu
Veaceslav
V
da Silva Filho
Demetrio A
DA
Friedlein
Rainer
R
Osikowicz
Wojciech
W
Murdey
Richard
R
Suess
Christian
C
Salaneck
William R
WR
Brédas
Jean-Luc
JL
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
D000873:Anthracenes; D009279:Naphthacenes; D009281:Naphthalenes; D011084:Polycyclic Aromatic Hydrocarbons; C031721:naphthalene; C034020:anthracene; C487736:naphthacene