A Concise Set of “Large”, Symmetric Molecules for Evaluation of Modern Computational Methods
A Concise Set of “Large”, Symmetric Molecules for Evaluation of Modern Computational Methods
复制标题
用于评估现代计算方法的一组简明“大”对称分子
DOI：
10.1021/jp011482j
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发表时间：
2001
影响因子：
2.9
通讯作者：
R. Pascal
中科院分区：
文献类型：
--
作者：
R. Pascal
利用各种从头算和混合密度泛函（HDFT）方法计算了一系列具有良好x射线数据的应变环内环的结构。发现HDFT方法系统地高估了这些分子的跨环非键接触距离。考虑到评估现代计算方法的现有测试集的缺陷，导致了一组具有精确已知几何形状的较大分子的编译。选择了20个高度对称的分子，这些分子存在高质量的x射线结构，分子位于高对称位点，分子间相互作用相对较弱。将这些分子的实验结构与5种计算方法[HF/3-21G（*）、MP2(FC)/6-31G(d)、B3LYP/6-31G(d)、B3PW91/6-31G(d)和B3PW91/cc-pVDZ]计算的结构进行了比较，并在选择常规几何优化计算方法的背景下对结果进行了讨论。
The structures of a series of strained in-cyclophanes, for which good X-ray data are available, were calculated by using a variety of ab initio and hybrid density functional (HDFT) methods. The HDFT methods were found to overestimate systematically the transannular nonbonded contact distances in these molecules. A consideration of the deficiencies of existing test sets for the evaluation of modern computational methods led to the compilation of a set of larger molecules with accurately known geometries. Twenty highly symmetric molecules were selected for which there exist high-quality X-ray structures where the molecules reside at high symmetry sites with only relatively weak intermolecular interactions. The experimental structures of these molecules were compared with the structures calculated by five computational methods [HF/3-21G(*), MP2(FC)/6-31G(d), B3LYP/6-31G(d), B3PW91/6-31G(d), and B3PW91/cc-pVDZ], and the results are discussed in the context of choosing computational methods for routine geometry optimizations.