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.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
小虎应助ye采纳,获得10
刚刚
无花果应助CHEN采纳,获得10
1秒前
张津浩完成签到,获得积分10
1秒前
辛晨晨关注了科研通微信公众号
1秒前
1秒前
Mecury完成签到,获得积分10
1秒前
冷月fan完成签到,获得积分10
2秒前
想不出来完成签到 ,获得积分10
2秒前
张丽妍发布了新的文献求助10
2秒前
希望天下0贩的0应助SUNSHINE采纳,获得10
3秒前
可爱皮皮虾完成签到,获得积分10
3秒前
4秒前
4秒前
满意芯发布了新的文献求助10
4秒前
张津浩发布了新的文献求助10
4秒前
4秒前
888完成签到,获得积分20
5秒前
优雅的涵瑶完成签到,获得积分10
5秒前
hmbb发布了新的文献求助10
5秒前
普外科老白完成签到,获得积分10
5秒前
manzhi关注了科研通微信公众号
5秒前
康德杰完成签到,获得积分10
5秒前
小爱完成签到,获得积分10
6秒前
kk完成签到,获得积分10
6秒前
6秒前
6秒前
7秒前
xy完成签到,获得积分10
7秒前
孤狼完成签到,获得积分10
8秒前
田様应助111采纳,获得10
8秒前
田様应助侯侯采纳,获得10
9秒前
9秒前
9秒前
9秒前
10秒前
寒冷半雪完成签到,获得积分10
10秒前
10秒前
11秒前
888发布了新的文献求助10
11秒前
11秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
Cognitive Neuroscience: The Biology of the Mind 1000
Technical Brochure TB 814: LPIT applications in HV gas insulated switchgear 1000
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
Picture Books with Same-sex Parented Families: Unintentional Censorship 500
Nucleophilic substitution in azasydnone-modified dinitroanisoles 500
不知道标题是什么 500
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 3969094
求助须知:如何正确求助?哪些是违规求助? 3514055
关于积分的说明 11171564
捐赠科研通 3249344
什么是DOI,文献DOI怎么找? 1794799
邀请新用户注册赠送积分活动 875377
科研通“疑难数据库(出版商)”最低求助积分说明 804779