Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I

原子轨道的线性组合 Atom(片上系统) 原子轨道 电子 部分电荷 原子物理学 人口 物理 计算化学 量子力学 化学 分子轨道 分子 嵌入式系统 有机化学 计算机科学 人口学 社会学
作者
Robert S. Mulliken
出处
期刊:Journal of Chemical Physics [American Institute of Physics]
卷期号:23 (10): 1833-1840 被引量:10348
标识
DOI:10.1063/1.1740588
摘要

With increasing availability of good all‐electron LCAO MO (LCAO molecular orbital) wave functions for molecules, a systematic procedure for obtaining maximum insight from such data has become desirable. An analysis in quantitative form is given here in terms of breakdowns of the electronic population into partial and total ``gross atomic populations,'' or into partial and total ``net atomic populations'' together with ``overlap populations.'' ``Gross atomic populations'' distribute the electrons almost perfectly among the various AOs (atomic orbitals) of the various atoms in the molecule. From these numbers, a definite figure is obtained for the amount of promotion (e.g., from 2s to 2p) in each atom; and also for the gross charge Q on each atom if the bonds are polar. The total overlap population for any pair of atoms in a molecule is in general made up of positive and negative contributions. If the total overlap population between two atoms is positive, they are bonded; if negative, they are antibonded.Tables of gross atomic populations and overlap populations, also gross atomic charges Q, computed from SCF (self‐consistent field) LCAO‐MO data on CO and H2O, are given. The amount of s‐p promotion is found to be nearly the same for the O atom in CO and in H2O (0.14 electron in CO and 0.15e in H2O). For the C atom in CO it is 0.50e. For the N atom in N2 it is 0.26e according to calculations by Scherr. In spite of very strong polarity in the π bonds in CO, the σ and π overlap populations are very similar to those in N2. In CO the total overlap population for the π electrons is about twice that for the σ electrons. The most easily ionized electrons of CO are in an MO such that its gross atomic population is 94% localized on the carbon atom; these electrons account for the (weak) electron donor properties of CO. A comparison between changes of bond lengths observed on removal of an electron from one or another MO of CO and H2, and corresponding changes in computed overlap populations, shows good correlation. Several other points of interest are discussed.
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