Charge-transfer transitions in triarylamine mixed-valence systems: a joint density functional theory and vibronic coupling study.
A theoretical model is developed to describe the intramolecular transfer in organic mixed-valence systems. It is applied to rationalize the intervalence charge-transfer transitions in triarylamine mixed-valence compounds. The electronic coupling parameter is evaluated at the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) levels. The shapes of the charge-transfer absorption bands are analyzed in the framework of a dynamic vibronic model. The influence on the optical properties of diagonal and nondiagonal vibronic couplings is discussed. Our results are compared to recent experimental data.
Coropceanu
V
V
Department of Chemistry, The University of Arizona, Tucson, Arizona 85721-0041, USA.
Malagoli
M
M
André
J M
JM
Brédas
J L
JL
D000588:Amines / Q000737:chemistry*; D004579:Electron Transport; D008956:Models, Chemical; D008958:Models, Molecular; D013057:Spectrum Analysis
D000588:Amines