电场作用下溴甲烷的光谱和解离特性

doi:10.19596/j.cnki.1001-246x.7736

计算物理 ›› 2018, Vol. 35 ›› Issue (5): 619-625.DOI: 10.19596/j.cnki.1001-246x.7736

电场作用下溴甲烷的光谱和解离特性

王啸卿^1,2, 刘玉柱^1,2, 尹文怡^1,2, 李金花^1,2

1. 南京信息工程大学江苏省大气与海洋光电探测重点实验室, 南京 210044;
2. 江苏省大气环境与装备技术协同创新中心, 南京 210044

收稿日期:2017-08-06 修回日期:2017-08-16 出版日期:2018-09-25 发布日期:2018-09-25
通讯作者: LIU Yuzhu,E-mail:yuzhu.liu@gmail.com
基金资助:
Project supported by the National Natural Science Foundation of China (Grant No. 11304157), Natural Science Foundation of the Higher Education Institutions of Jiangsu Province of China (Grant No.18KJA140002) and the State Key Laboratory of Artificial Microstructure and Mesoscopic Physics

Spectrum and Dissociation Characteristics of Methyl Bromide in External Electric Field

WANG Xiaoqing^1,2, LIU Yuzhu^1,2, YIN Wenyi^1,2, LI Jinhua^1,2

1. Jiangsu Key Laboratory for Optoelectronic Detection of Atmosphere and Ocean, Nanjing University of Information Science & Technology, Nanjing 210044, China;
2. Jiangsu Collaborative Innovation Center on Atmospheric Environment and Equipment Technology(CICAEET), Nanjing, 210044, China

Received:2017-08-06 Revised:2017-08-16 Online:2018-09-25 Published:2018-09-25
Supported by:
Project supported by the National Natural Science Foundation of China (Grant No. 11304157), Natural Science Foundation of the Higher Education Institutions of Jiangsu Province of China (Grant No.18KJA140002) and the State Key Laboratory of Artificial Microstructure and Mesoscopic Physics

摘要/Abstract

摘要： 采用了密度泛函理论（density functional theory，DFT），在6-311++G（d，p）基组水平上使用B3LYP方法研究外电场（0-0.05a.u.）对于溴甲烷分子的键长、能隙及解离势能面的影响.结果表明：外加电场的方向和大小对于分子结构和解离势能面均有显著的影响.随着负向外电场（Br-C键方向）从0增加到0.05a.u.，C-Br键的键长先减小后增大，C-H键的键长逐渐增加，分子能隙E_G逐渐减小，C-Br键的str振动频率逐渐增加而IR振动频率逐渐减小.进一步计算发现：随着正向外电场（C-Br键方向）从0增加到0.03a.u.，溴甲烷分子的势能曲线有所降低，解离势垒逐渐减小.因此，可以通过外电场来控制CH₃Br分子的降解.

关键词: 外电场, 解离, 密度泛函理论, 溴甲烷

Abstract: B3LYP/6-311++g(d,p) method is adopted to optimize ground state structure of CH₃Br molecule. Bond length, energy gap and dissociation potential energy surface of CH₃Br molecule in external electric field (0-0.05 a.u.) are studied. It shows that direction and magnitude of applied electric field is of great significance to molecular structure and potential energy surface. With negative electric field (C-Br bond direction) increases from 0 to 0.05 a.u., bond length of C-Br bond decreases first and then increases. Bond length of C-H bond increases gradually. Molecular energy gap E_G decreases gradually. Vibrational frequency of C-Br bond increases while IR vibration frequency decreases. It is found that potential energy of methyl bromide molecule decreases and dissociation barrier decreases, which indicating that CH₃Br molecule is easy to be excited and dissociated in external electric field.

Key words: external electric field, dissociation, DFT, methyl bromide

中图分类号:

O604

王啸卿, 刘玉柱, 尹文怡, 李金花. 电场作用下溴甲烷的光谱和解离特性[J]. 计算物理, 2018, 35(5): 619-625.

WANG Xiaoqing, LIU Yuzhu, YIN Wenyi, LI Jinhua. Spectrum and Dissociation Characteristics of Methyl Bromide in External Electric Field[J]. CHINESE JOURNAL OF COMPUTATIONAL PHYSICS, 2018, 35(5): 619-625.

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电场作用下溴甲烷的光谱和解离特性

Spectrum and Dissociation Characteristics of Methyl Bromide in External Electric Field

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