几种常见脂肪醇的氢键结构探究——红外光谱测定结合量化计算的实验

doi:10.3866/PKU.DXHX202210029

Abstract

Abstract:

Infrared spectroscopy has become a common method for analysis and characterization owing to its high sensitivity, high-speed measurement, and ability to obtain many information about functional groups. Although most of the experimental projects in existing textbooks focus on the qualitative and quantitative analysis of compounds, which are mainly based on infrared spectroscopy, there are few experimental investigations on infrared spectroscopy involving intermolecular hydrogen bonding and quantum chemical calculations. In this study, based on original infrared spectroscopy experiments, several common aliphatic alcohols were used as examples to investigate the infrared spectral characteristics of alcohol-carbon tetrachloride solutions with different percentages (V/V%). The hydrogen bond structures were explored in combination with quantum chemical calculations. The improved teaching method, combining macro and micro that is experimental phenomena and molecular structure respectively, may enable students to have a clearer understanding of the original frequency values of absorption peaks and the microscopic effect of intermolecular hydrogen bonds. In addition, it can significantly improve their interest in learning, broaden their horizons, and cultivate innovative thinking and critical thinking skills.

Key words: Infrared spectroscopy, Quantum chemical calculation, Aliphatic alcohol, Hydrogen bond, Macro and micro

Yu Liu, Jiming Zheng, Nayan Zongchen, Hong Wu, Wanqun Hu. Combining Infrared Spectroscopy Experiment with Quantum Chemical Calculations to Study Hydrogen Bond in Several Aliphatic Alcohol and CCl₄ Solutions[J].University Chemistry, 2023, 38(8): 216-224.

Figures/Tables 8

References 26

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输入文件	含义
%chk=Ethanol_1.chk	指定checkpoint文件名称
# opt freq b3lyp/6-31+g(d, p) scrf=(iefpcm, solvent=ccl4) geom=connectivity empiricaldispersion=gd3	指定计算方法，基组，溶剂，色散矫正
Ethanol	标题行
0 1	电荷与多重度
C −2.11475407 −1.13661207 0.00000000	分子说明部分，确定分子中各原子的坐标(此处为笛卡尔坐标)
H −1.75809964 −2.14542207 0.00000000
C −1.60141185 −0.41065579 1.25740497
H −0.53141366 −0.41236286 1.25838332
H −1.95646841 0.59871722 1.25642758
H −1.95968081 −0.91392379 2.13105517
H −3.18475407 −1.13659888 0.00000000
O −1.63807915 −0.46250981 −1.16759033
H −1.95641249 −0.91575292 −1.95170420

吸收峰位置/cm⁻¹	官能团
~3362.24	缔合羟基(O―H)的伸缩振动吸收峰
2969.90、2887.82	甲基(―CH₃)和亚甲基(―CH₂)的碳氢伸缩振动吸收峰
1452.25	―CH₂碳氢弯曲振动吸收
1375.10	―CH₃碳氢弯曲振动吸收
1088.64、1047.61	C―O伸缩振动吸收峰
790.02、758.23	C―Cl伸缩振动吸收峰

脂肪醇	单体	二聚体		环状三聚体	链状三聚体
脂肪醇	ν_OH	ν_{Bonded OH}	ν_{Free OH}	ν_{Bonded OH}	ν_{Bonded OH}	ν_{Free OH}
乙醇	3694.05	3483.45	3681.97	3371.02	3379.60	3689.36
				3432.15	3427.58
				3435.36
正丙醇	3695.95	3504.85	3695.36	3373.36	3376.25	3691.71
				3434.92	3425.34
				3436.91
异丙醇	3682.54	3487.77	3684.65	3358.66	3379.46	3678.86
				3417.03	3424.85
				3432.37
正丁醇	3694.99	3503.32	3694.27	3374.23	3380.12	3691.13
				3436.22	3428.25
				3436.83

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Combining Infrared Spectroscopy Experiment with Quantum Chemical Calculations to Study Hydrogen Bond in Several Aliphatic Alcohol and CCl₄ Solutions

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Combining Infrared Spectroscopy Experiment with Quantum Chemical Calculations to Study Hydrogen Bond in Several Aliphatic Alcohol and CCl₄ Solutions