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Performance of DFT Methods in the Calculation of Optical Spectra of TCF-Chromophores
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U.S. Army Research Laboratory, Aberdeen Proving Ground.
, ‡The Hebrew University of Jerusalem.
, §Pacific Northwest National Laboratory.
Section:Abstract
We present electronic structure calculations of the ultraviolet/visible (UV−vis) spectra of highly active push−pull chromophores containing the tricyanofuran (TCF) acceptor group. In particular, we have applied the recently developed long-range corrected Baer-Neuhauser-Livshits (BNL) exchange-correlation functional. The performance of this functional compares favorably with other density functional theory (DFT) approaches, including the CAM-B3LYP functional. The accuracy of UV−vis results for these molecules is best at low values of attenuation parameters (γ) for both BNL and CAM-B3LYP functionals. The optimal value of γ is different for the charge-transfer (CT) and π−π* excitations. The BNL and PBE0 exchange correlation functionals capture the CT states particularly well, while the π−π* excitations are less accurate and system dependent. Chromophore conformations, which considerably affect the molecular hyperpolarizability, do not significantly influence the UV−vis spectra on average. As expected, the color of chromophores is a sensitive function of modifications to its conjugated framework and is not significantly affected by increasing aliphatic chain length linking a chromophore to a polymer. For selected push−pull aryl-chromophores, we find a significant dependence of absorption spectra on the strength of diphenylaminophenyl donors.
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History
- Published In Issue October 13, 2009
- Article ASAPAugust 25, 2009
- Received: May 8, 2009
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