Benchmark of Simplified Time-Dependent Density Functional Theory for UV–Vis Spectral Properties of Porphyrinoids

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Contributors

Abstract

Time-dependent density functional theory is thoroughly benchmarked for the predictive calculation of UV–vis spectra of porphyrin derivatives. With the aim to provide an approach that is computationally feasible for large-scale applications such as biological systems or molecular framework materials, albeit performing with high accuracy for the Q-bands, the results given by various computational protocols, including basis sets, density-functionals (including gradient corrected local functionals, hybrids, double hybrids and range-separated functionals), and various variants of time-dependent density functional theory, including the simplified Tamm–Dancoff approximation, are compared. An excellent choice for these calculations is the range-separated functional CAM-B3LYP in combination with the simplified Tamm–Dancoff approximation and a basis set of double-ζ quality def2-SVP (mean absolute error [MAE] of ≈0.05 eV). This is not surpassed by more expensive approaches, not even by double hybrid functionals, and solely systematic excitation energy scaling slightly improves the results (MAE ≈0.04 eV).

Details

Original languageEnglish
Article number1900192
JournalAdvanced Theory and Simulations
Volume3
Issue number1
Publication statusPublished - 1 Jan 2020
Peer-reviewedYes

Keywords

Keywords

  • density functional theory, porphyrinoids, spectroscopy, UV–Vis