High level ab initio calculations at the B3LYP/6-311G(d,p) and MP2(full)/6-311G(d,p) levels employing PCM/UA0 model with different van der Waals' radii for the systems that contain lithium atoms have been carried out, in order to see if the van der Waal's radius for lithium atom employed in the default PCM/UA0 model is proper or not. Comparative analysis indicated that the van der Waals' radius for alkali metals, especially for lithium atom in the default PCM/UA0 model within the Gaussian 03 package, is too small, which causes erroneous redundant imaginary frequencies (RIFs) in the characterization of Li-containing compounds from moderate to big size. A new set of van der Waals' atomic radii based on QTAIM, proposed by Bader, was suggested for a better choice in the characterization of compounds containing alkali metals, for which it can effectively avoid the erroneous RIFs for corresponding geometries of these Li-containing systems. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem 108: 1422-1434, 2008

中文翻译：

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默认 PCM 模型中使用的范德华半径的测试和修改

在 B3LYP/6-311G(d,p) 和 MP2(full)/6-311G(d,p) 级别的高级 ab initio 计算采用具有不同范德华半径的 PCM/UA0 模型，用于包含锂的系统已执行原子，以查看默认 PCM/UA0 模型中使用的锂原子的范德华半径是否正确。对比分析表明，Gaussian 03 封装中默认的 PCM/UA0 模型中碱金属的范德华半径，尤其是锂原子的范德华半径太小，导致在表征 Li-含有中等至大尺寸的化合物。Bader 提出了一套基于 QTAIM 的新范德华原子半径，作为表征含碱金属化合物的更好选择，为此，它可以有效地避免这些含锂系统的相应几何形状的错误 RIF。© 2008 Wiley Periodicals, Inc. Int J Quantum Chem 108: 1422-1434, 2008