浅谈环张力对C＝C及C＝O双键红外吸收频率的影响

doi:10.3866/PKU.DXHX202209041

Abstract

Abstract:

Infrared spectroscopy is an important content of a college course "spectroscopy analysis", and the understanding of the influence of ring strain on infrared absorption frequency is a challenge. No rigorous and detailed explanation on this exists in the current textbooks, making students still confused when they accept the conclusion of the influence of ring strain on infrared vibrational frequency. Here, we use the density functional theory (DFT) to calculate the strain energy, bond length, bond angle, vibrational frequency, and orbital proportion of related bonds based on the fully optimized molecular structure. Based on the results of DFT calculation, the effect of ring strain on the vibrational frequencies of C＝C and C＝O double bonds is explained reasonably and in detail.

Key words: Infrared spectroscopy, Ring strain, Vibrational frequency, Density functional theory, Vibrational coupling

Yanchun Guo, Huiting Wang, Donghui Wei, Xiaolan Chen, Shuxia Cao. Brief Discussion of the Influence of Ring Strain on Infrared Absorption Frequencies of C＝C and C＝O Double Bonds[J].University Chemistry, 2023, 38(8): 305-311.

Figures/Tables 7

References 7

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化合物类型
ν_C＝C/cm⁻¹ (Calc.)	1669.92	1674.86	1698.24	1781.62
ν_C＝C/cm⁻¹ (Obs.)	1651	1657	1678	1780
Bond angle (θ)/(°)	122.88	125.80	133.89	148.39
C＝C Bond length/Å	1.336	1.333	1.329	1.322
s character in C＝C/%	37.86	40.09	42.82	47.90
p character in C＝C/%	62.11	59.88	57.15	52.07
Strain energy/(kJ∙mol⁻¹)	0.00	12.92	88.24	127.84

化合物类型
ν_C＝O/cm⁻¹ (Calc.)	1749.83	1776.92	1820.41	1882.48
ν_C＝O/cm⁻¹ (Obs.)	1715	1745	1780	1815
Bond angle (θ)/(°)	122.40	125.82	133.78	147.75
C＝O Bond length/Å	1.216	1.211	1.203	1.203

化合物类型
ν_C＝C/cm⁻¹ (Calc.)	1669.24	1635.66	1594.63	1686.52
ν_C＝C/cm⁻¹ (Obs.)	1646	1611	1566	1656
Bond angle (θ)/(°)	123.53	112.10	94.39	64.61
C＝C Bond length/Å	1.337	1.335	1.340	1.295
s character in C＝C/%	38.61	37.52	36.32	35.94
p character in C＝C/%	61.35	62.45	63.63	64.01
Strain energy/(kJ∙mol⁻¹)	0.00	10.19	105.97	202.30

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Brief Discussion of the Influence of Ring Strain on Infrared Absorption Frequencies of C＝C and C＝O Double Bonds

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