一氟二氯乙烷分子在外电场中的光谱特征和解离特性

doi:10.19596/j.cnki.1001-246x.8591

计算物理 ›› 2023, Vol. 40 ›› Issue (4): 453-460.DOI: 10.19596/j.cnki.1001-246x.8591

一氟二氯乙烷分子在外电场中的光谱特征和解离特性

刘启帆¹(), 闫好奎², 布玛丽亚·阿布力米提¹^,*(), 向梅¹^,*(), 安桓¹, 郑敬严¹

1. 新疆师范大学物理与电子工程学院, 新疆乌鲁木齐 830054
2. 新疆计量测试研究院, 新疆乌鲁木齐 830011

收稿日期:2022-07-13 出版日期:2023-07-25 发布日期:2023-10-13
通讯作者: 布玛丽亚·阿布力米提, 向梅
作者简介:
刘启帆(1998-)，男，硕士研究生，主要从事分子反应动力学方面的研究, E-mail：308698499@qq.com
基金资助:
国家自然科学基金(21763027); 新疆自治区杰出青年基金(2022D01E12); 新疆区域协同创新专项(2019E0223); 新疆高校科研项目(XJEDU2020Y029); 新疆研究生教育教学改革项目(XJ2021GY25); 新疆师范大学"十三五"校级重点学科招标项目(17SDKD0602); 新疆师范大学本科教学研究与改革项目(SDJG2021-12); 新兴污染物与生物标志物监测天山创新团队基金(2021D14017)

Spectral Characteristics and Dissociation Characteristics of Monofluorodichloroethane Molecule in External Electric Field

Qifan LIU¹(), Haokui YAN², Abulimiti BUMALIYA¹^,*(), Mei XIANG¹^,*(), Huan AN¹, Jingyan ZHENG¹

1. College of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi, Xinjiang 830054, China
2. Xinjiang Research Institute of Measurement & Testing, Urumqi, Xinjiang 830011, China

Received:2022-07-13 Online:2023-07-25 Published:2023-10-13
Contact: Abulimiti BUMALIYA, Mei XIANG

摘要/Abstract

摘要：

利用密度泛函理论在B3LYP/6-311+G(d, p)水平上研究不同外加电场下(-0.05~0.05 a.u.)一氟二氯乙烷分子的光谱特征和解离特性, 其中包括该分子基态结构、总能量、偶极矩、最高占据轨道能级、最低空轨道能级、能隙、红外光谱、拉曼光谱、紫外可见光吸收光谱及C原子与Cl原子间势能曲线等数据在电场下的变化趋势。在y轴方向上, 随着负向电场的增强, C原子与Cl原子核间距增长、最高占据轨道能级减小, 体系总能量、最低未占据轨道能级、能隙先增大后减小, 偶极矩先减小后增加。外加电场会影响一氟二氯乙烷分子红外光谱、拉曼光谱与紫外可见光吸收光谱的吸收强度和吸收峰频率, 红外光谱、拉曼光谱与紫外可见光吸收光谱随着电场变化出现红移或蓝移现象。C原子与Cl原子间势垒随着负向电场增加逐渐减小, 并在电场达到-0.05 a.u.时C原子与其中一个Cl原子发生断裂, 当分子中一个C—Cl键断裂后, 施加强度为-0.04 a.u.的电场时另外一个C—Cl键发生断裂, 分子在电场下发生逐步解离, 研究结果完善了一氟二氯乙烷分子受外电场影响的理论数据。

关键词: 一氟二氯乙烷, 密度泛函理论, 外电场, 光谱, 解离特性

Abstract:

Using density functional theory at B3LYP/6-311+G(d, p) level, the spectral characteristics and dissociation characteristics of (-0.05~0.05 a.u.) monofluorodichloroethane molecules under different applied electric fields are studied. It includes the ground state structure, total energy, dipole moment, highest occupied orbital energy level, lowest vacant orbital energy level, energy gap, infrared spectrum, Raman spectrum, UV-visible absorption spectrum and potential energy curve of between C and Cl bond under electric field. In the y-axis direction, with the increase of negative electric field, the distance between C atom and Cl nucleus increases, the highest occupied orbital energy level decreases, the total energy of the system, the lowest unoccupied orbital energy level and the energy gap increase first and then decrease, and the dipole moment decreases first and then increases. The applied electric field can affect the absorption intensity and absorption peak frequency of the infrared spectrum, Raman spectrum and UV-visible light absorption spectrum of monofluorodichloroethane. The infrared spectrum, Raman spectrum and UV-visible light absorption spectrum appear red shift or blue shift with the change of electric field. The barrier between C and Cl atoms gradually decreases with the increase of negative electric field and reaches -0.05 a.u. When C atom breaks with one of the Cl atoms, when a C—Cl bond in the molecule breaks, the applied strength is -0.04 a.u. When the electric field of, another C—Cl bond is broken, and the molecule is gradually dissociated under the electric field. The research results improve the theoretical data of the influence of external electric field on mono-fluorodichloroethane molecules.

Key words: monofluorodichloroethane, density functional theory, electric field, spectrum, dissociation characteristics

刘启帆, 闫好奎, 布玛丽亚·阿布力米提, 向梅, 安桓, 郑敬严. 一氟二氯乙烷分子在外电场中的光谱特征和解离特性[J]. 计算物理, 2023, 40(4): 453-460.

Qifan LIU, Haokui YAN, Abulimiti BUMALIYA, Mei XIANG, Huan AN, Jingyan ZHENG. Spectral Characteristics and Dissociation Characteristics of Monofluorodichloroethane Molecule in External Electric Field[J]. Chinese Journal of Computational Physics, 2023, 40(4): 453-460.

图/表 15

表1 不同基组计算得到的HCFC-141b分子稳定构型参数

Table 1 Stable configuration parameters of HCFC-141B molecule calculated by different basis groups

Method	R_C—F/nm	R_C—Cl/nm
B3LYP/6-311+G (d, p)	0.136	0.180
MPW1PW91/6-311+G (d, p)	0.135	0.178
MPW1PW91/3-21G	0.136	0.187
BYV86/6-311++G (d, p)	0.137	0.181
Ref.[11]	0.134	0.177

图1 优化后的HCFC-141b分子稳定结构

Fig.1 The optimized HCFC-141B molecular stability structure

图2 分子键长随外电场的变化

Fig.2 Molecular bond length varies with external electric field

图3 分子基态电荷布局随外电场变化的分布

Fig.3 The ground state charge distribution of a molecule varies with the external electric field

图4 分子偶极矩和能量随外电场的变化

Fig.4 Variation of molecular dipole moment and the total molecular energy with external electric field

图5 分子能级分布随外电场的变化

Fig.5 The variation of molecular energy level distribution and energy gap distribution with external electric field

图6 分子红外光谱计算值同实验值对比

Fig.6 Comparison between calculated value of molecular infrared spectrum and experimental value

图7 IR光谱在724 cm-1处吸收峰随外电场的变化

Fig.7 IR spectrum 724 cm-1 absorption peak with the change of external electric field

图8 IR光谱在906 cm-1处吸收峰随外电场的变化

Fig.8 IR spectrum 906 cm-1 absorption peak with the change of external electric field

图9 Raman光谱在3057.06、3132.98、3151.14 cm-1处吸收峰随负向电场的变化

Fig.9 Raman spectrum 3057.06、3132.98、3151.14 cm-1 absorption peak changes with negative external electric field

图10 Raman光谱在3057.06、3130.98、3151.14 cm-1处吸收峰随正向电场的变化

Fig.10 Raman spectrum 3057.06、3130.98、3151.14 cm-1 absorption peak changes with forward external electric field

图11 UV-Vis光谱吸收峰随外电场的变化

Fig.11 The variation of UV-Vis spectral absorption peak with external electric field

图12 5C—8Cl键势能曲线随外电场的变化

Fig.12 The potential energy curve of 5C—8Cl bond varies with external electric field

图13 C2H3FCl自由基的优化结构

Fig.13 Optimized structure of C2H3FCl radical

图14 5C—7Cl键势能曲线随外电场的变化

Fig.14 The potential energy curve of 5C—7Cl bond varies with external electric field

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一氟二氯乙烷分子在外电场中的光谱特征和解离特性

Spectral Characteristics and Dissociation Characteristics of Monofluorodichloroethane Molecule in External Electric Field

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