Validation of Local Hybrid Functionals for Excited States: Structures, Fluorescence, Phosphorescence, and Vibronic Spectra

Journal of Chemical Theory and Computation
Robin Grotjahn, Martin Kaupp

Abstract

Local hybrid functionals are evaluated in linear-response TDDFT computations for a broad range of excited-state properties including excited-state structures, fluorescence, and phosphorescence energies and the vibronic shape of absorption and phosphorescence spectra. Computation of such properties requires the optimization of excited states, which is facilitated by the recent implementation of excited-state gradients for local hybrid functionals in the TURBOMOLE program (Grotjahn, R.; Furche, F.; Kaupp, M. J. Chem. Theory Comput. 2019, 15, 5508). Comparison with coupled-cluster reference values reveals competitive performance of local hybrids for excited-state bond lengths with particular advantages for carbon-halogen, carbon-carbon, and carbon-nitrogen bonds. As with most global and range-separated hybrid functionals, carbonyl and thionyl bonds in n → π* excited states are found to be too compact. For the emission energies, results depend on the multiplicity of the excited state. While the local hybrid functionals tested perform moderately well, comparable to global hybrids, for singlet states (fluorescence energies), they provide outstanding accuracy for triplet states (phosphorescence energies), only matched by those from th...Continue Reading

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Citations

Mar 2, 2021·Physical Chemistry Chemical Physics : PCCP·Pau Besalú-SalaMiquel Solà
Aug 6, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Muhammet Erkan Köse
Sep 8, 2020·The Journal of Physical Chemistry. a·Robin GrotjahnMartin Kaupp

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