期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 111, 期 44, 页码 11269-11277出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp0715023
关键词
-
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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据