分子轨道理论概念：基础与拓展

doi:10.3866/PKU.DXHX202207022

Abstract

Abstract:

Molecular orbital theory is an important chemical bonding theory and also a difficult point in the study of general chemistry. In this article, the problems often encountered by beginners of molecular orbital theory are sorted out and analyzed, and the application of molecular orbital theory is expanded. By tracing the formation and development of the molecular orbital theory, combined with the requirements of the Chemistry Olympiad test questions, summarization and analysis are carried out to deepen the understanding of the molecular orbital theory and promote the teaching of the molecular orbital theory.

Key words: Molecular orbital, Electron configuration, Energy level diagram, Chemical bond

Zihao Liu. Molecular Orbital Theory: Basics and Expansion[J].University Chemistry, 2023, 38(5): 335-340.

Figures/Tables 9

References 19

1	沈玉龙; 杨笑春; 刘立华. 化学通报, 2019, (4), 379.
2	Werner K. Angew. Chem. Int. Ed. 1996, 35, 573.
3	沈玉龙; 杨笑春; 舒世立; 刘立华. 化学通报, 2018, (7), 667.
4	Robert S. M. J. Chem. Phys. 1935, 3, 375.
5	张祖德. 无机化学, 第2版合肥: 中国科学技术大学出版社, 2008, 219
6	华彤文; 王颖霞; 卞江; 陈景祖. 普通化学原理, 第4版北京: 北京大学出版社, 2013, 301- 302.
7	北京师范大学; 华中师范大学; 南京师范大学. 无机化学(上册), 第5版北京: 高等教育出版社, 2020, 88- 89.
8	宋天佑; 程鹏; 徐佳宁; 张丽荣. 无机化学(上册), 第4版北京: 高等教育出版社, 2019, 215- 216.
9	周公度; 段连运. 结构化学基础, 第5版北京: 北京大学出版社, 2017, 84- 85.
10	麦松威; 周公度; 王颖霞; 张羽伸. 高等无机结构化学, 第3版北京: 北京大学出版社, 2021, 70- 72.
11	徐光宪; 王祥云. 物质结构, 第2版北京: 科学出版社, 2010, 158- 160.
12	Catherine, E. H.; Alan, G. S. Inorganic Chemistry, 5th ed.; Pearson: New York, NY, USA, 2018; p. 40.
13	Gaty, L. M.; Paul, J. F.; Donald, A. T. Inorganic Chemistry, 5th ed.; Pearson: New York, NY, USA, 2018; p. 117.
14	Duward, S.; Mark, W.; Tina, O.; Jonathan, R.; Fraser A. Inorganic Chemistry, 6th ed.; W. H. Freeman and Company: New York, NY, USA, 2014; p. 44.
15	Bicelhaupt F. M. ; Nagle J. K. ; Klemm W. L. J. Phys. Chem. A 2008, 112, 2437. doi: 10.1021/jp710328f
16	Ryan J. M. ; Jarred J. B. ; Mark N V. W. ; Brandon J. B. ; Douglas A. V. G. ; Roger L D. J. Chem. Educ. 2011, 88, 1094. doi: 10.1021/ed100758t
17	Calculated Data navigation (nist. gov). [2022-09-14]. https://webbook.nist.gov/chemistry/
18	Myles J. D. ; Jeffrey D. S. ; Anthony M. M. ; Curtis E. M. ; Arnold L. R. ; Michael L. M. ; Joshua S. F. Science 2019, 363, 1203. doi: 10.1126/science.aaw6102
19	浙江省化学会. 决胜化学奥林匹克, 北京: 化学工业出版社, 2021, 70

实例	O₂的电子组态	参考文献
1	(σ_1s)²(σ_1s^)²(σ_2s)²(σ_2s^)²(σ_2p)²(π_2p)⁴(π_2p^*)²	[5]
2	(σ_1s)²(σ_1s^)²(σ_2s)²(σ_2s^)²(σ_{2p_x})²(π_{2p_y})²(π_{2p_z})²(π_{2p_y}^)¹(π_{2p_z}^)¹	[6–10]
3	(σ_g2p)² (π_u2p)⁴(π_g^*2p)² (价电子组态)	[10]
4	(σ_g1s)²(σ_u^1s)²(σ_g2s)²(σ_u^2s)²(σ_g2p)²(π_u2p_x)²(π_u2p_y)²(π_g^2p_x)¹(π_g^2p_y)¹	[11]
5	σ_g(2s)²σ_u^(2s)²σ_g(2p_z)²π_u(2p_x)²π_u(2p_y)²π_g^(2p_x)¹π_g^*(2p_y)¹ (价电子组态)	[12]
6	σ_g²π_u²π_u²π_g^1π_g^1(2p) (p电子组态)	[13]
7	1σ_g²1σ_u²2σ_g²1π_u⁴1π_g⁴ (价电子组态)	[14]

物种	电子组态	N―N键长/pm	键级^a
N₂	KK(σ_2s)²(σ_2s^*)²(π_{2p_y})²(π_{2p_z})²(σ_{2p_x})²	109.78	3
N₂⁺(σ_{2p_x})	KK(σ_2s)²(σ_2s^*)²(π_{2p_y})²(π_{2p_z})²(σ_{2p_x})¹	111.6	2.5
N₂⁺(π_2p)	KK(σ_2s)²(σ_2s^*)²(π_{2p_y})¹(π_{2p_z})²(σ_{2p_x})²	117.6	2.5
N₂⁺(σ_2s^*)	KK(σ_2s)²(σ_2s^*)¹(π_{2p_y})²(π_{2p_z})²(σ_{2p_x})²	107.5	3.5

实例	CO的电子组态	参考文献
1	(1σ)²(2σ)²(3σ)²(4σ)²(1π)⁴(5σ)²	[6, 8, 11, 14]
2	(1σ)²(2σ)²(1π)⁴(3σ)² (价电子组态)	[9]
3	(1σ)²(1σ^*)²(1π)⁴(2σ)² (价电子组态)	[10]
4	(1σ)²(1σ^)²(2σ)²(2σ^)²(1π)⁴(3σ)²	[11]

实例	HF的电子组态	参考文献
1	(1σ^non)²(2σ^non)²(3σ)²(1π^non)⁴	[5]
2	(σ_2s)²(σ)²(1π_2p)⁴ (价电子组态)	[6]
3	(2s)²(σ)²(2p_x)²(2p_y)² (价电子组态)	[9]
4	K(2s)² (2p_x)²(2p_y)²(σ)²	[11]
5	2s²σ_z²π_xⁿ²π_yⁿ² (价电子组态)	[10]
6	(1σ)²(2σ)²(3σ)²(1π)²(2π)²	[8]

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Molecular Orbital Theory: Basics and Expansion

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