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Choose Your Level Wisely : Assessing Density Functionals and Dispersion Corrections for Metal Carbonyl Compounds

Glitz, Vinícius LU orcid ; Port, Vinícius Capriles ; Nordlander, Ebbe LU ; Peralta, Rosely Aparecida and Caramori, Giovanni Finoto (2025) In Journal of Computational Chemistry 46(27).
Abstract

Understanding the structure of metal-ligand complexes is essential for catalyst design, materials development, and biochemical modeling. Metal carbonyls are especially relevant due to their diverse structures and electronic features. Here, we benchmarked seventeen density functionals (B3LYP, BP86, CAM–B3LYP, M06, M06L, PBE, PBE0, r2SCAN, r2SCAN–3c, revPBE, revTPSS, RPBE, TPSS, TPSS0, TPSSh, (Formula presented.) B97, and (Formula presented.) B97X) combined with three dispersion schemes (D3zero, D3BJ, D4) and also tested calculations without dispersion correction, totaling fifty-four approaches. Their ability to reproduce geometries, structural parameters, and CO stretching frequencies was assessed for thirty-four... (More)

Understanding the structure of metal-ligand complexes is essential for catalyst design, materials development, and biochemical modeling. Metal carbonyls are especially relevant due to their diverse structures and electronic features. Here, we benchmarked seventeen density functionals (B3LYP, BP86, CAM–B3LYP, M06, M06L, PBE, PBE0, r2SCAN, r2SCAN–3c, revPBE, revTPSS, RPBE, TPSS, TPSS0, TPSSh, (Formula presented.) B97, and (Formula presented.) B97X) combined with three dispersion schemes (D3zero, D3BJ, D4) and also tested calculations without dispersion correction, totaling fifty-four approaches. Their ability to reproduce geometries, structural parameters, and CO stretching frequencies was assessed for thirty-four Mn(I) and Re(I) carbonyls obtained from the CCDC. Relative electronic energies were further compared using DLPNO-CCSD(T) calculations, alongside evaluation of computational cost. Our results highlight that hybrid meta-GGA and meta-GGA functionals, particularly TPSSh(D3zero) and r2SCAN(D3BJ, D4), offer the best balance between accuracy and efficiency, providing reliable structures, vibration properties, and energetics consistent with high-level DLPNO-CCSD(T) references.

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author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
dispersion corrections, DLPNO-CCSD(T), KS-DFT, manganese(I), rhenium(I)
in
Journal of Computational Chemistry
volume
46
issue
27
article number
e70245
publisher
John Wiley & Sons Inc.
external identifiers
  • scopus:105018281344
  • pmid:41069255
ISSN
0192-8651
DOI
10.1002/jcc.70245
language
English
LU publication?
yes
id
9f890787-0e7c-4781-8f64-ae9530d0a9eb
date added to LUP
2026-01-12 15:53:59
date last changed
2026-01-13 03:00:08
@article{9f890787-0e7c-4781-8f64-ae9530d0a9eb,
  abstract     = {{<p>Understanding the structure of metal-ligand complexes is essential for catalyst design, materials development, and biochemical modeling. Metal carbonyls are especially relevant due to their diverse structures and electronic features. Here, we benchmarked seventeen density functionals (B3LYP, BP86, CAM–B3LYP, M06, M06L, PBE, PBE0, r<sup>2</sup>SCAN, r<sup>2</sup>SCAN–3c, revPBE, revTPSS, RPBE, TPSS, TPSS0, TPSSh, (Formula presented.) B97, and (Formula presented.) B97X) combined with three dispersion schemes (D3zero, D3BJ, D4) and also tested calculations without dispersion correction, totaling fifty-four approaches. Their ability to reproduce geometries, structural parameters, and CO stretching frequencies was assessed for thirty-four Mn(I) and Re(I) carbonyls obtained from the CCDC. Relative electronic energies were further compared using DLPNO-CCSD(T) calculations, alongside evaluation of computational cost. Our results highlight that hybrid meta-GGA and meta-GGA functionals, particularly TPSSh(D3zero) and r<sup>2</sup>SCAN(D3BJ, D4), offer the best balance between accuracy and efficiency, providing reliable structures, vibration properties, and energetics consistent with high-level DLPNO-CCSD(T) references.</p>}},
  author       = {{Glitz, Vinícius and Port, Vinícius Capriles and Nordlander, Ebbe and Peralta, Rosely Aparecida and Caramori, Giovanni Finoto}},
  issn         = {{0192-8651}},
  keywords     = {{dispersion corrections; DLPNO-CCSD(T); KS-DFT; manganese(I); rhenium(I)}},
  language     = {{eng}},
  number       = {{27}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Journal of Computational Chemistry}},
  title        = {{Choose Your Level Wisely : Assessing Density Functionals and Dispersion Corrections for Metal Carbonyl Compounds}},
  url          = {{http://dx.doi.org/10.1002/jcc.70245}},
  doi          = {{10.1002/jcc.70245}},
  volume       = {{46}},
  year         = {{2025}},
}