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Some properties of transition metal compounds can be influenced by static correlation, relativistic effects, and, in some cases, close-lying electronic states could result in difficulties in SCF convergence. All these complications influence geometry optimizations and, hence, the accuracy of the obtained results.

Considering a usual Kohn-Sham DFT calculation of a TM compound with organic ligands:

  1. What functionals gives accurate equilibrium geometries, compared to high-level calculations or experimental ones?
  2. What functionals are accurate for electronic and bonding properties?

I'm not asking for a specific functional, but some guidelines on which are better for those purposes.

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    $\begingroup$ This seems very much like an opinion question. I'd consider how you could reformulate it in a more objective way - for example, what functionals are accurate for geometries or thermochemistry of transition metal + ligand complexes. $\endgroup$
    – Geoff Hutchison
    Apr 30, 2020 at 20:58
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    $\begingroup$ @GeoffHutchison is the current version better? $\endgroup$
    – Verktaj
    Apr 30, 2020 at 22:34
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    $\begingroup$ I like the question, but I think it should probably be split into 3 questions to avoid being too broad (plus it never hurts to have more questions). $\endgroup$
    – Tyberius ♦
    May 1, 2020 at 16:24
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    $\begingroup$ @Verktaj - it's a better question, but I agree with Tyberius that I'd split it - perhaps just on geometries and bonding? Then I'd suggest a separate questions about spectra or NMR $\endgroup$
    – Geoff Hutchison
    May 1, 2020 at 23:38
  • $\begingroup$ Since you might already know which research area specifically you are looking for within, a search in chemical reviews, accounts of chemical research, or any other review articles should summarize for you as to which functional does a good job for your purposes. $\endgroup$
    – gogo
    May 24, 2020 at 2:06

2 Answers 2

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The general question on the accuracy of density functionals for transition metal compounds is highly ambigious due to the effect of static correlation, for which there is no solution at the moment.

As to the simpler question on well-behaving TM compounds with organic ligands, a benchmark study on transition metal reaction barrier heights found that Head-Gordon's recent functionals are excellent choices, with revTPSS0-D4 also faring well.

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I think for transition metals the best functionals would be MS1-D3(0), ωB97M-V, ωB97X-V, MN15, and B97M-r based on the information from the review article-Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals

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