Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Ragnar Bjornsson, Michael Buehl

Research output: Contribution to journalArticlepeer-review

23 Citations (Scopus)

Abstract

Electric field gradients (EFGs) were computed for the first-row transition metal nuclei in Cr(C6H6)(CO)(3), MnO3F, Mn(CO)(5)H, MnCp(CO)(3), Co(CO)(4)H, Co(CO)(3)(NO) and VCp(CO)(4), for which experimental gas-phase data (in form of nuclear quadrupole coupling constants) are available from microwave spectroscopy. A variety of exchange-correlation functionals were assessed, among which range-separated hybrids (such as CAM-B3LYP or LC-omega PBE) perform best, followed by global hybrids (such as B3LYP and PBE0) and gradient-corrected functionals (such as BP86). While large basis sets are required on the metal atom for converged EFGs, smaller basis sets can be employed on the ligands. In most cases, EFGs show little sensitivity toward the geometrical parameters.

Original languageEnglish
Pages (from-to)5319-5324
Number of pages6
JournalDalton Transactions
Volume39
Issue number22
Early online date4 May 2010
DOIs
Publication statusPublished - Jun 2010

Keywords

  • NMR chemical-shifts
  • Cyclopentadienyl manganese tricarbonyl
  • Gaussian-basis sets
  • Molecular-structure
  • Microwave measurements
  • Vanadium chloroperoxidase
  • Correlation-energy
  • QM/MM models
  • Gas
  • Accuracy

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