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Performance of new exchange–correlation functionals in providing vertical excitation energies of metal complexes

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Abstract

The performance of Hartree–Fock and twenty-three exchange–correlation functionals from Density Functional Theory was evaluated by means of experimental values of vertical excitation energies in metal complexes (tetraoxos, carbonyls, and halides) by using augmented basis sets of two different sizes, double- and triple-\(\zeta\). The analysis is carried out in terms of linear correlation parameters, that is, coefficients of determination and slope errors. In general, the results present only a small dependency with the basis set size. Range-separated hybrids (RSHs), mainly by LC-PBEPBE and LC-QTP, show the best performance for tetraoxo complexes. In addition, all methods provide poor results for carbonyls, where functionals from Local Density Approximation and Generalized Gradient Approximation (GGA) are better, followed by hybrids and RSHs. Moreover, hybrids, hybrid meta-GGAs (except for M06-HF), and mainly RSHs are more successful for halide complexes. Finally, considering all systems together, the functionals that provide the largest coefficients of determination (R2 \(\ge\) 0.98) along with the smallest slope errors (Error(\(\alpha\)) < 0.08) are the RSHs, except for CAM-QTP-00. This comparative investigation should contribute to future studies regarding the general analysis of optical properties in metal complexes.

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Acknowledgements

RLAH is grateful to The São Paulo Research Foundation (FAPESP) for financial support (2014/23714-1) and to National Council for Scientific and Technological Development (CNPq) for a research grant (301211/2018-3). RAM thanks the Center for Mathematical Sciences Applied to Industry (CeMEAI) – FAPESP 2013/07375-0 for computational resources. This research was supported in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior Brasil (CAPES)—Finance Code 001.

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    Rodrigo Araújo Mendes & Roberto Luiz Andrade Haiduke

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Mendes, R.A., Haiduke, R.L.A. Performance of new exchange–correlation functionals in providing vertical excitation energies of metal complexes. Theor Chem Acc 140, 146 (2021). https://doi.org/10.1007/s00214-021-02844-8

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