草酰氯分子光谱和解离动力学：外电场效应研究

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摘要

草酰氯是一种高毒性、高腐蚀性的挥发性有机化合物，其广泛存在于人类生产和生活中。本文采用密度泛函理论的B3LYP方法，在6-311+ G (d, p)基组水平下研究了外加电场对键长、键能、偶极矩和解离机理的影响。结果表明，在外电场作用下，草酰氯的一个碳氯键(C1-Cl3)增加，另一个碳氯键(C4-Cl6)则减少；同时，碳碳键的键长随着电场的增大而逐渐增大。分子总能量随电场的增大而减小，偶极矩则随电场的增大而增大。在红外光谱中，碳氯(C4-Cl6)键的振动频率降低，而碳氧键的振动频率增加。在紫外可见光谱中，最强吸收峰的波长随外加电场的增大而增大，并出现了明显的红移现象。此外，本文还利用EOM-CCSD法扫描了草酰氯在碳碳键上的单点能量，得到了不同电场下的势能曲线。随着外加电场的增大，碳碳键的断裂使势能曲线中的解离势垒减小。本文研究结果为进一步研究草酰氯的性质提供了参考，为研究草酰氯的降解提供了理论依据。

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	尹文怡
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	布玛丽亚·阿布力米提

关键词 ： oxalyl chloride, spectra, electric field, density functional theory, degradation

Abstract：

Oxalyl chloride is a highly toxic and caustic substance, which widely exists in human production and life as a kind of volatile organic compound. Based on the density functional theory B3LYP at 6-311++G (d, p) level, the influences of external electric field on the bond length, bond energy, dipole moment and dissociation mechanism are optimized. The results indicate that the C1–Cl3 bond length increases while the C4–Cl6 bond decreases. At the same time, the carbon-carbon bond length gradually increases with the increase of electric field. The total energy decreases while the dipole moment gradually increases with the increase of electric field. In the infrared spectra, the vibration frequency of the carbon-chlorine (C4–Cl6) bond decreases while the vibration frequency of the carbon-oxygen bond increases. In the ultraviolet-visible spectra, the wavelength of the strongest absorption peak increases as the external electric field increases and shows an observable red shift phenomenon. Additionally, single point energies of oxalyl chloride along the carbon-carbon bond are scanned with the equation-of-motion coupled cluster method restricted to single and double excitations (EOM-CCSD) method and the potential energy curves under different external electric fields are obtained. The dissociation barrier in potential energy curve decreases because of the breakage of carbon-carbon bond with the increase of external electric field. These results provide reference for further researches on the properties of oxalyl chloride and offer a theoretical basis for the study of oxalyl chloride degradation.

Key words： oxalyl chloride spectra electric field density functional theory degradation

收稿日期: 2018-07-25 出版日期: 2019-04-12

基金资助:

This project was supported by the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province of China (No. 18KJA140002), National Natural Science Foundation of China (Nos. 11564040, 21763027), Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX18_1015), and Undergraduate Training Program for Innovation and Entrepreneurship (Nos. 201710762008, 201710762055)

通讯作者: yuzhu.liu@gmail.com and maryam917@xjnu.edu.cn E-mail: yuzhu.liu@gmail.com and maryam917@xjnu.edu.cn

引用本文:

尹文怡;刘玉柱;周冯斌;布玛丽亚·阿布力米提. 草酰氯分子光谱和解离动力学：外电场效应研究[J]. 结构化学, 2019, 38(4): 499-508.
YIN Wen-Yi;LIU Yu-Zhu;ZHOU Feng-Bin;BUMALIYA Abulimiti. Molecular Spectra and Dissociation Dynamics of Oxalyl Chloride: Effect of External Electrical Fields. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2019, 38(4): 499-508.

链接本文:

http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2019/V38/I4/499

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