Zubarev Dmitry Yu, Boldyrev Alexander I
Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-0300, United States of America.
Phys Chem Chem Phys. 2008 Sep 14;10(34):5207-17. doi: 10.1039/b804083d. Epub 2008 Jul 3.
A method of description of the chemical bonding combining the compactness and intuitive simplicity of Lewis theory with the flexibility and generality of canonical molecular orbital theory is presented, which is called adaptive natural density partitioning. The objects of chemical bonding in this method are n-center 2-electron bonds, where n goes from one (lone-pair) to the maximum number of atoms in the system (completely delocalized bonding). The algorithm is a generalization of the natural bonding orbital analysis and is based on the diagonalization of the blocks of the first-order density matrix in the basis of natural atomic orbitals. The results obtained by the application of the algorithm to the systems with non-classical bonding can be readily interpreted from the point of view of aromaticity/antiaromaticity concepts. The considered examples include Li4 cluster and a family of planar boron clusters observed in molecular beams.
提出了一种化学键描述方法，它将路易斯理论的简洁性和直观性与正则分子轨道理论的灵活性和通用性相结合，称为自适应自然密度划分。该方法中化学键的研究对象是n中心2电子键，其中n从1（孤对电子）到系统中原子的最大数目（完全离域键）。该算法是自然键轨道分析的推广，基于自然原子轨道基组下一阶密度矩阵块的对角化。将该算法应用于具有非经典键的体系所得到的结果，可从芳香性/反芳香性概念的角度很容易地进行解释。所考虑的例子包括Li4团簇和在分子束中观察到的一族平面硼团簇。
