摘要
利用密度泛函理论(Density functional theory,DFT)在B3LYP/6-311++G(d,声)水平上研究了外电场(-15.43~15.43V/nm)对氟利昂F13(三氟氯甲烷,CRCl)分子物理和光谱特性的影响.计算结果表明,在C~Cl键连线z方向上,外电场从-15.43V/nm逐渐增加到15.43V/nm时,分子体系能量先增大后降低,偶极矩表现为先减小后增大,能隙ElG先增加后减小,C-Cl键键长逐渐增大,C-F键键长逐渐减小.外电场对CRCl分子红外振动光谱的频率和强度也有影响.进一步研究发现在外电场作用(O到15.43V/nm)逐渐增强下,CRCl分子的势能曲线束缚形态逐渐被解开,解离的势垒逐渐减小.在强度为15.43V/nm的电场作用下,CF3Cl分子将会发生C-C1键断裂而降解,该结果为对氟利昂进行外电场降解提供重要的参考依据.
Density functional theory (DFT) at B3LYP/6-311q-q-G(d,p) level is used for the investi- gation of physical properties and spectra of Freon 13 (CF3C1) in external electric field. Calculated re- sults show that, with increasing the external field from --15.43 to 15.43 V/nm along the molecular axis z gradually, and total energy first increases and then decreases, while dipole moment decreases at the beginning and then increases. Energy gaps increases and then decreases. C--C1 bond length in- creases while C--F bond length decreases. At the same time, the trend of vibrational frequency and intensity of molecular IR spectra in external electric field are also explored. Further studies show that with increasing gradually the external electric field from 0 to 15.43 V/nm, the dissociation PES along C--C1 bond becomes unbond with disappearing of the dissociation barrier. In the external electric field of 15.43 V/nm, CF3C1 occurs degradation with breaking of C--C1 bond. Such results provide an im- portant reference for the degradation of freon in the external electric field.
作者
李相鸿
刘玉柱
陈云云
尹文怡
林华
布玛丽亚·阿布力米提
LI Xiang-hong;LIU Yu-zhu;CHEN Yun-yun;YIN Wen-yi;LIN Hua;ABULIMITI Bumaliya(Jiangsu Key Laboratory for Optoelectronic Detection of Atmosphere and Ocean, Nanjing University of Information Science ~ Tech nology, Nanjing 210044, Chinas;Institute of Clinical Pharmacology, Yijishan Hospital of Wannan Medical College, Wuhu 241001, China;Jiangsu Collaborative Innovation Center on Atmospheric Environment and Equipment Technology (CICAEET), Nanjing 210044, China;School of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054,China)
出处
《分子科学学报》
CAS
CSCD
北大核心
2018年第2期139-143,共5页
Journal of Molecular Science
基金
国家自然科学基金资助项目(11564040)
关键词
氟利昂
外电场
降解
光谱
DFT
freon
external electronic field
degradation
spectra
DFT