Quantitative Computational Thermochemistry of Transition Metal Species

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This article discusses quantitative computational thermochemistry of transition metal species. The correlation consistent Composite Approach (ccCA), which has been shown to achieve chemical accuracy (±1 kcal mol⁻¹) for a large benchmark set of main group and s-block metal compounds, is used to compute enthalpies of formation for a set of 17 3d transition metal species.

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9 p.

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DeYonker, Nathan J.; Peterson, Kirk A.; Steyl, Gideon; Wilson, Angela K. & Cundari, Thomas R., 1964- May 15, 2007.

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This article discusses quantitative computational thermochemistry of transition metal species. The correlation consistent Composite Approach (ccCA), which has been shown to achieve chemical accuracy (±1 kcal mol⁻¹) for a large benchmark set of main group and s-block metal compounds, is used to compute enthalpies of formation for a set of 17 3d transition metal species.

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9 p.

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Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2007 American Chemical Society.

The correlation consistent Composite Approach (ccCA), which has been shown to achieve chemical accuracy (±1 kcal mol⁻¹) for a large benchmark set of main group and s-block metal compounds, is used to compute enthalpies of formation for a set of 17 3d transition metal species. The training set includes a variety of metals, ligands, and bonding types. Using the correlation consistent basis sets for the 3d transition metals, the authors find that gas-phase enthalpies of formation can be efficiently calculated for inorganic and organometallic molecules with ccCA. However, until the reliability of gas-phase transition metal thermochemistry is improved, both experimentally and theoretically, a large experimental training set where uncertainties are near ±1 kcal mol⁻¹ (akin to commonly used main group benchmarking sets) remains an ambitious goal. For now, an average deviation of ±3 kcal mol⁻¹ appears to be the initial goal of "chemical accuracy" for ab initio transition metal model chemistries. The ccCA is also compared to a more robust but relatively expensive composite approach primarily utilizing large basis set coupled cluster computations. For a smaller training set of eight molecules, ccCA has a mean absolute deviation (MAD) of 3.4 kcal mol⁻¹ versus the large basis set coupled-cluster-based model chemistry, which has a MAD of 3.1 kcal mol⁻¹. However, the agreement for transition metal complexes is more system dependent than observed in previous benchmark studies of composite methods and main group compounds.

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  • Journal of Physical Chemistry A, 2007, Washington DC: American Chemical Society, pp. 11269-11277

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 111
  • Issue: 44
  • Page Start: 11269
  • Page End: 11277
  • Peer Reviewed: Yes

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  • May 15, 2007

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  • Oct. 9, 2012, 10:02 a.m.

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  • July 23, 2013, 10:50 a.m.

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DeYonker, Nathan J.; Peterson, Kirk A.; Steyl, Gideon; Wilson, Angela K. & Cundari, Thomas R., 1964-. Quantitative Computational Thermochemistry of Transition Metal Species, article, May 15, 2007; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107799/: accessed October 17, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.