Center for Bioinformatics and Institute of Physical Chemistry, University of Hamburg, Bundesstraße 43, D-20146 Hamburg, Germany.
J Phys Chem A. 2013 Apr 4;117(13):2879-83. doi: 10.1021/jp401495u. Epub 2013 Mar 21.
In a recent paper, Xu et al. [J. Phys. Chem. A 2012, 116, 11668] emphasized the importance of core-electron correlation effects to describe the Si2H6BH3 complex and related systems properly. Unexpected large energy differences between a frozen core and all electron treatment were observed. In the present study, it will be shown that these energy differences are an artifact of an insufficient choice of basis set and can be attributed to an intramolecular basis set superposition error (BSSE). Although the general problem is known, systematic studies on the effect are scarce. Therefore, the BSSE in related systems is investigated. This study shows that the problem of BSSE for core-electron correlation is quite common if inadequate basis sets are applied and that it amounts to 2 kcal mol(-1) on average in binding energies for the given test set (with a maximum of 5.8 kcal mol(-1)).
在最近的一篇论文中，Xu 等人强调了描述 Si2H6BH3 配合物和相关体系时考虑芯电子相关效应的重要性。他们观察到冻结芯和全电子处理之间存在出乎意料的大能量差异。在本研究中，将表明这些能量差异是基组选择不当的人为产物，可归因于分子内基组叠加误差 (BSSE)。尽管该普遍问题是已知的，但对其影响的系统研究很少。因此，研究了相关体系中的 BSSE。该研究表明，如果应用不充分的基组，芯电子相关的 BSSE 问题非常普遍，并且对于给定的测试集，BSSE 在结合能中平均达到 2 kcal mol(-1)（最大值为 5.8 kcal mol(-1)）。
