Department of Quantum Chemistry, Nicolaus Copernicus University, 7-Gagarina St., PL-87 100 Toruń, Poland.
J Phys Chem A. 2010 Dec 2;114(47):12498-505. doi: 10.1021/jp106740e. Epub 2010 Nov 4.
The influence of various small- and medium-size basis sets used in Hartree-Fock (HF) and density functional theory (DFT)/B3LYP calculations on results of quantum theory of atoms in molecules based (QTAIM-based) analysis of bond parameters is investigated for several single, double, and triple covalent bonds. It is shown that, in general, HF and DFT/B3LYP methods give very similar QTAIM results with respect to the basis set. The smallest 6-31G basis set and DZ-quality basis sets of Dunning type lead to poor results in comparison to those obtained by the most reliable aug-cc-pVTZ. On the contrary, 6-311++G(2df,2pd) and in a somewhat lesser extent 6-311++G(3df,3pd) basis sets give satisfactory values of QTAIM parameters. It is also demonstrated that QTAIM calculations may be sensitive for the method and basis set in the case of multiple and more polarized bonds.
研究了在 Hartree-Fock（HF）和密度泛函理论（DFT）/B3LYP 计算中使用的各种中小基组对基于原子在分子中量子理论（QTAIM）的键参数分析的结果的影响，涉及几个单键、双键和三键。结果表明，一般来说，HF 和 DFT/B3LYP 方法在基组方面给出了非常相似的 QTAIM 结果。与最可靠的 aug-cc-pVTZ 相比，最小的 6-31G 基组和 Dunning 类型的 DZ 质量基组导致结果较差。相反，6-311++G(2df,2pd)和在较小程度上的 6-311++G(3df,3pd)基组给出了令人满意的 QTAIM 参数值。还表明，在存在多个和更极化的键的情况下，QTAIM 计算可能对方法和基组敏感。
