A complete basis set model chemistry. VII. Use of the minimum population localization method
A complete basis set model chemistry. VII. Use of the minimum population localization method
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DOI：
10.1063/1.481224
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发表时间：
2000-04-15
影响因子：
4.4
通讯作者：
Petersson, GA
中科院分区：
文献类型：
--
作者：
Montgomery, JA;Frisch, MJ;Petersson, GA
结果表明，局部化对于保持分子能量非线性外推中的尺寸一致性是必要的。我们证明了从扩展基组波函数获得的 Mulliken 布居的非物理行为可能导致 Pipek-Mezey 布居定位方法对轨道的不完全定位，并引入了一种修改来纠正这个问题。新的定位程序称为最小群体定位，已纳入 CBS-QB3 和新的 CBS-4M 模型化学中，并在 G2/97 测试集上评估它们的性能。 CBS-QB3 的误差与 G3 和 G3(MP2) 的误差相当（G2/97 测试集的平均绝对偏差分别为 1.10、0.94 和 1.21 kcal/mol）。 CBS-4M 的准确度低于其他模型（G2/97 测试集上的平均绝对偏差为 3.26 kcal/mol），但可以应用于更大的系统。改进的定位方法解决了 CBS-4 中发现的几个问题，并提高了 CBS-QB3 的可靠性。 (C) 2000 年美国物理研究所。 [S0021-9606(00)31015-7]。
It is shown that localization is necessary to preserve size consistency in nonlinear extrapolations of molecular energies. We demonstrate that the unphysical behavior of Mulliken populations obtained from extended basis set wave functions can lead to incomplete localization of orbitals by the Pipek-Mezey population localization method, and introduce a modification to correct this problem. The new localization procedure, called minimum population localization, is incorporated into the CBS-QB3 and the new CBS-4M model chemistries, and their performance is assessed on the G2/97 test set. The errors found for CBS-QB3 are comparable with those for the G3 and G3(MP2) (mean absolute deviation of 1.10, 0.94, and 1.21 kcal/mol, respectively, on the G2/97 test set). The CBS-4M is less accurate than the other models (mean absolute deviation of 3.26 kcal/mol on the G2/97 test set), but can be applied to much larger systems. The modified localization method resolves several problem cases found with CBS-4 and improves the reliability of CBS-QB3. (C) 2000 American Institute of Physics. [S0021-9606(00)31015-7].