Performance of DFT methods in the calculation of optical spectra of TCF-chromophores

Jan Andzelm*, Berend C. Rinderspacher, Adam Rawlett, Joseph Dougherty, Roi Baer, Niranjan Govind

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

54 Scopus citations


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.

Original languageAmerican English
Pages (from-to)2835-2846
Number of pages12
JournalJournal of Chemical Theory and Computation
Issue number10
StatePublished - Oct 2009


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