Calculation of Fukui functions without differentiating to the number of electrons. 3. Local Fukui function and dual descriptor
Calculation of Fukui functions without differentiating to the number of electrons. 3. Local Fukui function and dual descriptor
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DOI：
10.1021/ct800027e
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发表时间：
2008-07-01
影响因子：
5.5
通讯作者：
Geerlings, Paul
中科院分区：
文献类型：
--
作者：
Fievez, Tim;Sablon, Nick;Geerlings, Paul
计算基于dft的反应性描述符的另一种方法涉及能量与电子数和外部势的导数，进一步评估。利用对外部势的泛函导数，避免了局部计算Fukui函数和对偶描述子的有限差分逼近。在优化计算参数后，计算出相应的一组分子。结果表明，该方法能准确预测CH2O的亲核攻击、CO金属配合物的形成、单取代苯的区域选择性以及一些亲核试剂中最软的亲核位点。
An alternative approach for the calculation of DFT-based reactivity descriptors involving derivatives of the energy with respect to the number of electrons and the external potential is further evaluated. Using functional derivatives with respect to the external potential, the finite difference approximation was avoided for the local calculation of the Fukui functions and the dual descriptor. A relevant set of molecules has been calculated after the optimization of computational parameters. It is shown that the new approach correctly predicts the nucleophilic attack on CH2O, the formation of CO metal complexes, the regioselectivity of monosubstituted benzenes, and the softest nucleophilic site in some ambident nucleophiles.