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Long wavelength absorbing carbostyrils as test cases for different TDDFT procedures and solvent models

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Abstract

The vertical excitation energies of 3,4-dicyano-6-methoxy and 3,4-dicyano-6,7-dimethoxy carbostyril have been computed with different approximations for the time-dependent density functional theory (TD-DFT) procedure and with different implementations of the continuum solvation model COSMO. Different DFT functionals were tested in TD-DFT and Tamm-Dancoff approximations (TDA) for the excitation energies in the gas phase. TDA-B3LYP showed the best agreement with the experimental data. Then TDA-B3LYP computations were performed combined with the COSMO model of solvation comparing a linear response (LR) and a post-configuration interaction (CI) implementation of the fast solvent reorganization. The post-CI solvent model overestimates the π→π* transitions and strongly underestimates the n→π* transition. The TDA approximation in combination with the linear response implementation of the COSMO solvation model perfectly computes the experimental results. TDA-LR is the most reliable method for the computation of the vertical excitation energies in a solvent. Comparison with explicit solvent calculations shows there is only a minor effect on the energies of the electronic interaction of the solute with the solvent.

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Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9/I, 8010, Graz, Austria

    Anne-Marie Kelterer

  2. Institute of Chemistry, University of Graz, Heinrichstraße 28, 8010, Graz, Austria

    Georg Uray & Walter M. F. Fabian

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  1. Anne-Marie Kelterer
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  2. Georg Uray
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  3. Walter M. F. Fabian
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Correspondence to Anne-Marie Kelterer.

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This paper belongs to Topical Collection 9th European Conference on Computational Chemistry (EuCo-CC9)

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Kelterer, AM., Uray, G. & Fabian, W.M.F. Long wavelength absorbing carbostyrils as test cases for different TDDFT procedures and solvent models. J Mol Model 20, 2217 (2014). https://doi.org/10.1007/s00894-014-2217-5

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