Charge-Transfer Transitions in Triarylamine Mixed-Valence Systems: A Joint Density Functional Theory and Vibronic Coupling Study

Abstract
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.

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