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四氯化碳和二硫化碳中乙醇构象异构体布居的羟基伸缩振动拉曼光谱
胡乃银1, 林珂*1,2, 周晓国1,2, 刘世林*1
1.中国科学技术大学化学物理系,合肥微尺度物质科学国家实验室,合肥230026;2.中国科学技术大学量子信息与量子科技前沿协同创新中心,合肥230026
摘要:
综合利用拉曼光谱和密度泛函理论研究了乙醇在四氯化碳、二硫化碳溶液中乙醇构象异构体的布居. 首先确定了transgauche构象乙醇在OH伸缩振动拉曼光谱中的归属,然后结合理论计算的拉曼散射截面估计了两个异构体的能级差。 可以看出在四氯化碳和二硫化碳中trans乙醇更稳定。通过分析不同温度的拉曼光谱,发现范霍夫方程在这里并不适用. 利用玻尔兹曼分布律和理论拉曼散射截面,发现了两个异构体的能级差随着温度升高而增大,这反映了溶剂与乙醇之间越弱的分子间相互作用更有利于trans构象乙醇的布居。
关键词:  拉曼光谱,乙醇,构象异构体,能级差
DOI:10.1063/1674-0068/28/cjcp1503048
分类号:
基金项目:
Populations of Ethanol Conformers in Liquid CCl4 and CS2 by Raman Spectra in OH Stretching Region (cited:2)
Nai-yin Hu1, Ke Lin*1,2, Xiao-guo Zhou1,2, Shi-lin Liu*1
1.Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China;2.Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei 230026, China
Abstract:
Combining Raman spectroscopy with density functional theory, the populations of the trans- and gauche- ethanol conformers are investigated in carbon tetrachloride (CCl4) and carbon disulfide (CS2). The spectral contributions of two ethanol conformers are identified in OH stretching region. The energy difference between both conformers is estimated with the aid of the calculated Raman cross sections. It can be seen that the trans- ethanol is more stable in CCl4 and CS2 solutions. The spectra are also obtained at different temperatures, and it is found the van't Hoff analysis is invalid in these solutions. By taking accounts of the Boltzmann distribution and theoretical Raman cross section, the energy difference is found to be increased with temperature, which shows the weak intermolecular interactions can enhance the population of trans- ethanol.
Key words:  Raman spectroscopy, Ethanol, Conformer, Energy difference