Tognetti Vincent, Joubert Laurent
Normandy Univ. COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan, Cedex, France.
Chemphyschem. 2017 Oct 6;18(19):2675-2687. doi: 10.1002/cphc.201700637. Epub 2017 Aug 9.
Herein, we discuss three methods to partition the total molecular energy into additive atomic contributions within the framework of Bader's atoms-in-molecules theory and in the particular context of Kohn-Sham density functional theory. The first method is derived from the virial theorem, whereas the two other schemes, termed "standard" and "model", are based on Pendás' interacting-quantum-atoms decomposition. The methods are then compared for a dataset of molecules of interest for direct application in organic chemistry and biochemistry. Finally, the relevance of the three methods for the prediction of intrinsic reactivity properties (e.g., electrophilicity) or for unravelling the nature of chemical bonding (e.g., in halogen bonds, beyond the pure electrostatic point of view), is examined and paves the way for their more systematic use for the in silico design of new reactants.
在此，我们讨论了三种在巴德分子中的原子理论框架内，特别是在科恩-沙姆密度泛函理论背景下，将总分子能量划分为可加性原子贡献的方法。第一种方法源自维里定理，而另外两种方法，即“标准”法和“模型”法，是基于彭达斯的相互作用量子原子分解法。然后，针对一系列在有机化学和生物化学中有直接应用价值的感兴趣分子数据集，对这些方法进行了比较。最后，研究了这三种方法对于预测内在反应性质（如亲电性）或阐明化学键本质（如在卤键中，超越纯粹静电观点）的相关性，为它们在新反应物的计算机辅助设计中更系统地应用铺平了道路。
