氯乙烷在外电场中的解离性质

doi:10.19596/j.cnki.1001-246x.8686

摘要/Abstract

摘要：

选择B3LYP计算方法, 使用6-311G ++(d, p)基组, 计算在外加电场(0~10.28 V·nm^-1)作用下氯乙烷分子的结构特征和解离特性。计算结果表明: 随着电场强度增大, 分子的总能量增大, 碳碳单键键长呈减小趋势, 碳氯单键键长呈增大趋势, 偶极矩逐渐增大, 能隙先增大后减小, 红外吸收峰在不同频率下分别发生红移和蓝移, 拉曼峰强度变化。随着外电场增大, 势垒逐渐降低, 当外电场达到18.00 V·nm^-1时, 势垒几乎消失, 实现电场降解。

关键词: 氯乙烷, 外电场, 降解

Abstract:

Using B3LYP calculations on the 6-311G ++ (d, p) group, the structural characteristics and dissociation properties of the chloroethane molecule are discussed from the perspective of molecular structure under an external electric field (0~10.28 V·nm^-1). The calculation results show that with the increase of external electric field, the total energy of the molecule increases, the bond length of the C—C single bond decreases, the bond length of the C—Cl bond increases, the dipole moment increases, the size of the energy gap bond increases and then decreases. At different frequencies, the infrared absorption peaks respectively have red shift and blue shift phenomena, and the intensity of the Raman peaks changes. In addition, with the increase of the external electric field, the dissociation energy gradually decreases, and it can be seen that the potential energy barrier almost no longer exists when the external electric field reaches 18.00 V·nm^-1, representing that the degradation of the chloroethane has been achieved.

Key words: chloroethane, external electric field, degradation

中图分类号:

O561

唐静, 张昕阳, 江一航, 金鑫, 刘玉柱. 氯乙烷在外电场中的解离性质[J]. 计算物理, 2023, 40(6): 712-717.

Jing TANG, Xinyang ZHANG, Yihang JIANG, Xin JIN, Yuzhu LIU. Study on Dissociation Properties of Chloroethane Under External Electric Field[J]. Chinese Journal of Computational Physics, 2023, 40(6): 712-717.

图/表 10

表1 不同基组和方法优化后的氯乙烷分子的基态结构和实验值

Table 1 The ground state structure of CH3CH2Cl molecule optimized by different basis sets and methods with experimental value

Method	DFT B3LYP 6-311G ++(d，p)	DFT B3LYP 6-311G	DFT B3LYP 6-31G	DFT B3LYP 3-21G	DFT B3LYP 3-21G +^*	Exp.^[23]
R_{1, 2}/nm	0.151 6	0.150 9	0.151 2	0.152 0	0.152 6	0.151 0
R_{2, 8}/nm	0.182 4	0.188 5	0.188 5	0.191 7	0.182 0	0.178 9
R_{1, 4}/nm	0.109 2	0.107 9	0.108 1	0.109 3	0.108 2	0.108 9
R²	0.999 593 872	0.997 035 708	0.997 064 748	0.994 823 484	0.999 546 143

图1 氯乙烷分子基态稳定结构(其中箭头表示外加电场方向。)

Fig.1 Stable structure of the ground state of CH3CH2Cl molecule (The arrow indicates the direction of the external electric field.)

表2 氯乙烷分子键长和键角的理论值和实验值

Table 2 The theoretical value and experimental value of bond length and bond angle

Method	DFT B3LYP 6-311G ++(d，p)	Exp.^[23]
R_{1, 3}/nm	0.109 5	0.109 0
R_{1, 5}/nm	0.109 1	0.109 0
R_{2, 6}/nm	0.108 9	0.108 6
R_{2, 7}/nm	0.108 9	0.108 6
∠C₁C₂Cl	112.18	111.02
∠H₄C₁C₂	111.20	110.53
∠H₃C₁C₂	109.28	109.30
∠H₇C₂C₁	112.18	111.81
∠H₄C₁H₅	108.48	108.26
∠H₆C₂H₇	109.14	108.99

图2 不同外加电场下氯乙烷分子碳碳单键和碳氯单键的键长变化

Fig.2 Bond length changes of carbon-carbon single bond and carbon-chlorine single bond under different external fields

图3 不同外加电场下氯乙烷分子能量和偶极矩的变化

Fig.3 Changes of energy and dipole moment under different external fields

图4 不同外加电场下氯乙烷分子EL、EH和EG的变化

Fig.4 Changes of EL, EH and EG under different external fields

图5 不同外加电场下氯乙烷分子的红外吸收光谱图

Fig.5 Infrared absorption spectra of CH3CH2Cl molecule under different external fields

图6 氯乙烷分子实验和理论计算的红外光谱图

Fig.6 The experimental IR spectrum and calculated IR spectrum of CH3CH2Cl molecule

图7 不同外加电场下氯乙烷分子的拉曼光谱图

Fig.7 Raman spectra of CH3CH2Cl molecule under different external fields

图8 氯乙烷分子碳氯单键在不同电场下的单点扫描势能

Fig.8 Single point scanning potential energy of carbon-chlorine single bond of CH3CH2Cl molecule under different electric fields

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