title: Performance of DFT Methods in the Calculation of Optical Spectra of TCF-Chromophores.
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.
authors.affiliation: U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005, Institute of Chemistry and Fritz Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352.
authors.forename: Jan
authors.initials: J
authors.lastname: Andzelm
authors.affiliation: U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005, Institute of Chemistry and Fritz Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352.
authors.forename: Berend C
authors.initials: BC
authors.lastname: Rinderspacher
authors.affiliation: U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005, Institute of Chemistry and Fritz Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352.
authors.forename: Adam
authors.initials: A
authors.lastname: Rawlett
authors.affiliation: U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005, Institute of Chemistry and Fritz Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352.
authors.forename: Joseph
authors.initials: J
authors.lastname: Dougherty
authors.affiliation: U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005, Institute of Chemistry and Fritz Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352.
authors.forename: Roi
authors.initials: R
authors.lastname: Baer
authors.affiliation: U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005, Institute of Chemistry and Fritz Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, and William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352.
authors.forename: Niranjan
authors.initials: N
authors.lastname: Govind