Quantitative computational thermochemistry of transition metal species

被引:149
作者
DeYonker, Nathan J.
Peterson, Kirk A.
Steyl, Gideon
Wilson, Angela K.
Cundari, Thomas R. [1 ]
机构
[1] Univ N Texas, Dept Chem, CASCaM, Denton, TX 76203 USA
[2] Washington State Univ, Dept Chem, Pullman, WA 99164 USA
[3] Univ Orange Free State, Dept Chem, ZA-9301 Bloemfontein, South Africa
关键词
D O I
10.1021/jp0715023
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The correlation consistent Composite Approach (ccCA), which has been shown to achieve chemical accuracy (+/- l 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, we 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 complexcs is more system dependent than observed in previous benchmark studies of composite methods and main group compounds.
引用
收藏
页码:11269 / 11277
页数:9
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