Department of Chemistry and Ames Laboratory USDOE, Iowa State University, Ames, Iowa 50011, USA.
J Chem Phys. 2013 Dec 21;139(23):234107. doi: 10.1063/1.4840776.
Through a basis-set-independent web of localizing orbital-transformations, the electronic wave function of a molecule is expressed in terms of a set of orbitals that reveal the atomic structure and the bonding pattern of a molecule. The analysis is based on resolving the valence orbital space in terms of an internal space, which has minimal basis set dimensions, and an external space. In the internal space, oriented quasi-atomic orbitals and split-localized molecular orbitals are determined by new, fast localization methods. The density matrix between the oriented quasi-atomic orbitals as well as the locations of the split-localized orbitals exhibit atomic populations and inter-atomic bonding patterns. A correlation-adapted quasi-atomic basis is determined in the external orbital space. The general formulations are specified in detail for Hartree-Fock wave functions. Applications to specific molecules exemplify the general scheme.
通过一个基组无关的局域轨道变换网络，分子的电子波函数可以用一组轨道来表示，这些轨道揭示了分子的原子结构和键合模式。该分析基于根据内部空间和外部空间将价轨道空间展开，内部空间具有最小的基组维数。在内部空间中，通过新的快速局域化方法确定定向准原子轨道和分裂局域分子轨道。定向准原子轨道之间的密度矩阵以及分裂局域轨道的位置表现出原子的布居和原子间的键合模式。在外轨道空间中确定了一个相关自适应准原子基。详细说明了 Hartree-Fock 波函数的一般公式。对特定分子的应用例证了一般方案。
