Ruedenberg Klaus
Ames Laboratory and Department of Chemistry, USDOE, Iowa State University, Ames, Iowa 20011, USA.
J Chem Phys. 2022 Jul 14;157(2):024111. doi: 10.1063/5.0094609.
The chemical model of matter consists of atoms held together by bonds. The success of this model implies that the physical interactions of the electrons and nuclei in molecules combine into compound interactions that create the bonding. In the quantum mechanical description, the modified atoms in molecules and the bonding synergism are contained in the molecular electronic wave function. So far, only part of this information has been recovered from the wave function. Notably, the atoms have remained unidentified in the wave function. One reason is that conventional energy decomposition analyses formulate separate model wave functions, independent of the actual wave function, to represent "prepared atoms" and preconceived interactions and, then, intuitively catenate the parts. In the present work, the embedded modified atoms and the inherent physical synergisms between them are determined by a unified derivation entirely from the actual molecular valence space wave function. By means of a series of intrinsic orbital and configurational transformations of the wave function, the energy of formation of a molecule is additively resolved in terms of intra-atomic energy changes, interference energies, and quasi-classical, non-classical, and charge-transfer Coulombic interactions. The analysis furnishes an algorithm for the quantitative resolution of the energy of formation, which enables analyses elucidating reaction energies.
物质的化学模型由通过化学键结合在一起的原子组成。该模型的成功意味着分子中电子和原子核的物理相互作用结合成产生化学键的复合相互作用。在量子力学描述中，分子中经过修正的原子和键合协同作用包含在分子电子波函数中。到目前为止，仅从波函数中恢复了部分此类信息。值得注意的是，原子在波函数中仍未被识别出来。一个原因是传统的能量分解分析会构建独立于实际波函数的单独模型波函数，以表示“准备好的原子”和先入为主的相互作用，然后直观地将各部分连接起来。在本工作中，嵌入的经过修正的原子及其之间固有的物理协同作用完全由实际分子价空间波函数通过统一推导来确定。通过对波函数进行一系列本征轨道和构型变换，分子形成能可根据原子内能量变化、干涉能以及准经典、非经典和电荷转移库仑相互作用进行加和分解。该分析提供了一种用于定量解析形成能的算法，从而能够进行阐明反应能量的分析。
