Performance of Density Functional Theory for 3d Transition Metal-Containing Complexes: Utilization of the Correlation Consistent Basis Sets

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Article discussing the performance of density functional theory for 3d transition metal-containing complexes and the utilization of the correlation consistent basis sets.

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8 p.

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Tekarli, Sammer M.; Drummond, Michael L.; Williams, T. Gavin; Cundari, Thomas R., 1964- & Wilson, Angela K. July 2, 2009.

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Article discussing the performance of density functional theory for 3d transition metal-containing complexes and the utilization of the correlation consistent basis sets.

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8 p.

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Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2009 American Chemical Society.

Abstract: The performance of 44 density functionals used in conjunction with the correlation consistent basis sets (ccpVnZ where n = T and Q) has been assessed for the gas-phase enthalpies of formation at 298.15 K of 3d transition metal (TM) containing systems. Nineteen molecules were examined: ScS, VO, VO₂, Cr(CO)₆, MnS, MnCl₂, Mn(CO)₅Cl, FeCl₃, Fe(CO)₅, CoH(CO)₄, NiCl₂, Ni(CO)₄, CuH, CuF, CuCl, ZnH, ZnO, ZnCl, and Zn(CH₃)₂. Of the functionals examined, the functionals that resulted in the smallest mean absolute deviation (MAD, in parentheses, kcal molˉ¹) from experiment were B97-1(6.9), PBE1KCIS (8.1), TPSS1KCIS (9.6), B97-2(9.7), and B98(10.7). All five of these functionals include some degree of Hartree-Fock (HF) exchange. The impact of increasing the basis set from cc-pVTZ to cc-pVQZ was found to be slight for the generalized gradient approximation (GGA) and meta-GGA (MGGA) functionals studied, indicating basis set saturation at the triple-ζ level. By contrast, for most of the generalized gradient exchange (GGE), hybrid GGA (HGGA), and hybrid meta-GGA (HMGGA) functionals considered, improvements in the average MAD of 2-3 kcal molˉ¹ were seen upon progressing to a quadruple-ζ level basis set. Overall, it was found that the functionals that include Hartree-Fock exchange performed best overall, but those with greater than 40% HF exchange exhibit significantly poor performance for the prediction of enthalpies of formation for 3d TM complexes. Carbonyl-containing complexes, a mainstay in organometallic TM chemistry, are demonstrated to be exceedingly difficult to describe accurately with all but 2 of the 44 functionals considered. The most accurate functional, for both CO-containing and CO-free compounds, is B97-1/cc-pVQZ, which is shown to be capable of yielding results within 1 kcal molˉ¹ of high-level ab initio composite methodologies.

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  • Journal of Physical Chemistry A, 2009, Washington DC: American Chemical Society, pp. 8607-8614

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 113
  • Issue: 30
  • Page Start: 8607
  • Page End: 8614
  • Peer Reviewed: Yes

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  • July 2, 2009

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  • Oct. 14, 2012, 9:37 p.m.

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  • May 16, 2014, 12:01 p.m.

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Tekarli, Sammer M.; Drummond, Michael L.; Williams, T. Gavin; Cundari, Thomas R., 1964- & Wilson, Angela K. Performance of Density Functional Theory for 3d Transition Metal-Containing Complexes: Utilization of the Correlation Consistent Basis Sets, article, July 2, 2009; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc109722/: accessed August 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.