Theoretical Spectroscopy of Carbocyanine Dyes Made Accurate by Frozen Density Correction to Excitation Energies Obtained by TD-DFT

    Authors

    A. E. Masunov

    Comments

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    Abbreviated Journal Title

    Int. J. Quantum Chem.

    Keywords

    time-dependent density functional theory; conjugated dyes; absorption; wavelength; delta-SCF; FUNCTIONAL THEORY; ABSORPTION-SPECTRA; ELECTRONIC-SPECTRA; ORGANIC-DYES; PERFORMANCE; THERMOCHEMISTRY; EXCHANGE; Chemistry, Physical; Mathematics, Interdisciplinary Applications; Physics, Atomic, Molecular & Chemical

    Abstract

    We present long-awaited answer to the puzzling question of why the TD-DFT fails to predict the excitation energies in polymethine dyes accurately. The density functional theory methods were suspected to be inaccurate due to self interaction error inherent in exchange-correlation potentials. Here we decisively show that it is the linear response approximation that is responsible for these inaccuracies. Next, we use frozen density to evaluate the excitation energy beyond the linear response and increase the accuracy of the predictions. This recipe uniformly improves the accuracy of the first absorption maxima prediction in cyanine homologous series to within 25 nm. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110: 3095-3100, 2010

    Journal Title

    International Journal of Quantum Chemistry

    Volume

    110

    Issue/Number

    15

    Publication Date

    1-1-2010

    Document Type

    Article

    Language

    English

    First Page

    3095

    Last Page

    3100

    WOS Identifier

    WOS:000283761900038

    ISSN

    0020-7608

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